Oligofluorinated cross-linked polymers and uses thereof

ABSTRACT

The invention features oligofluorinated cross-linked polymers and their use in the manufacture of articles and coating surfaces.

BACKGROUND OF THE INVENTION

The invention features oligofluorinated cross-linked polymers. Oncecured, the oligofluorinated cross-linked polymers are useful as a basepolymer in the manufacture of articles or as a fluorinated coating.

Polymeric materials have been widely used for the manufacturing ofmedical devices, such as artificial organs, implants, medical devices,vascular prostheses, blood pumps, artificial kidneys, heart valves,pacemaker lead wire insulation, intra-aortic balloons, artificialhearts, dialyzers and plasma separators, among others. The polymer usedwithin a medical device must be biocompatible (e.g., must not producetoxic, allergic, inflammatory reactions, or other adverse reactions). Itis the physical, chemical and biological processes at the interface,between the biological system and the synthetic materials used, whichdefines the short- and long-term potential applications of a particulardevice.

In general, the exact profile of biocompatibility, biodegradation andphysical stability, including chemical and physical/mechanicalproperties i.e., elasticity, stress, ductility, toughness, timedependent deformation, strength, fatigue, hardness, wear resistance, andtransparency for a biomaterial are extremely variable. A wide variety ofpolymers (including polycondensates, polyolefins, polyvinyls,polypeptides, and polysaccharides, among others) have been employed inthe manufacture of biomedical devices, drug delivery vehicles, andaffinity chromatography systems. Polymers are selected for thecharacteristics that make them useful in any given application.

Fluoropolymers are generally hydrolytically stable and are resistant todestructive chemical environments. In addition they are biocompatibleand have been used as components of medical devices. The combination ofchemical inertness, low surface energy, antifouling properties,hydrophobicity, thermal and oxidative stability have enabled a greatdiversity of application for these materials. Fluoropolymers have beenprepared from tetrafluoroethylene, via chain growth polymerizationreactions, and other fluorinated derivatives, via step growthpolymerization reactions producing infinite network fluoropolymers. Achallenge for the use of these polymers in certain applications is theprocessing limitation of working with solid material including, (e.g.,fluorinated polyetherurethanes, made from polyether glycols,isocyanates, chain extenders and non-fluorinated polyols) rather thanfluids, of which the latter are easily applied into molds or ontosurfaces. The problem is even more difficult and almost impossible tomanage when the above needs to be cross linked for specificapplications. The demand and need for practical fluoropolymers withspecific chemical and physical properties has directed the moleculardesign and development of new fluorinated monomers

There exists a need for co-polymer systems, which can be designed toprovide the above characteristics that are needed for a variety ofapplications, including those in the biomedical field.

SUMMARY OF THE INVENTION

The invention features oligofluorinated cross-linked polymers. Oncecured, the oligofluorinated cross-linked polymer is useful as a basepolymer in the manufacture of articles or as an oligofluorinatedcoating. The coatings of the invention can also be used to encapsulatetherapeutic agents.

Accordingly, in a first aspect the invention features a monomerincluding (i) two or more cross-linking domains, and (ii) an oligomericsegment having a first end covalently tethered to a first cross-linkingdomain and a second end covalently tethered to a second cross-linkingdomain, wherein at least one of the cross-linking domains is anoligofluorinated cross-linking domain.

In certain embodiments, the monomer is further described by formula (I):

(D)-[(oligo)-(D)]_(n)   (I)

In formula (I) oligo is an oligomeric segment; each D is a cross-linkingdomain; and n is an integer from 1 to 20, 1 to 15, 1 to 10, 1 to 8, oreven 1 to 5, and wherein at least one D is an oligofluorinatedcross-linking domain.

In other embodiments, the monomer is further described by formula (II):

(D)-[(oligo)-(LinkA-F_(T))]_(m)[(oligo)-(D)]_(n)   (II)

In formula (II) oligo is an oligomeric segment; each D is across-linking domain; F_(T) is an oligofluoro group; each LinkA-F_(T) isan organic moiety covalently bound to a first oligo, a second oligo, andF_(T); n is an integer from 1 to 20; and m is an integer from 1 to 20,wherein at least one D is an oligofluorinated cross-linking domain.

Cross-linking domains which can be used in the compositions of theinvention include a reactive moiety that capable of chain growthpolymerization, such as, without limitation, vinyls, epoxides,aziridines, and oxazolines.

In still other embodiments, the oligofluorinated cross-linking domain isselected from

In certain embodiments, the monomer is further described by formula(III):

(oligo)_(n)(vinyl)_(m)(F_(T))_(o)   (III)

In formula (III) oligo is an oligomeric segment; vinyl is across-linking domain including an unsaturated moiety capable ofundergoing radical initiated polymerization; F_(T) is an oligofluorogroup covalently tethered to the vinyl and/or the oligo; and each of n,m, and o is, independently, an integer from 1 to 5, wherein the monomerincludes at least one oligofluorinated cross-linking domain. The monomerof formula (III) may further be described by formula (IV):

In formula (IV) oligo is an oligomeric segment; vinyl is a cross-linkingdomain including an unsaturated moiety capable of undergoing radicalinitiated polymerization; F_(T) is an oligofluoro group; each LinkA is,independently, an organic moiety covalently bound to oligo, F_(T), andvinyl; and a, b, and c are integers greater than 0.

In certain embodiments, the monomers of the invention include one ormore biologically active agents covalently tethered to the monomer.

In a related aspect, the invention features a method for coating anarticle by (a) contacting the article with a monomer of the inventionand (b) polymerizing the monomer to form a cross-linked coating.

In another aspect the invention features a method for making a shapedarticle by (a) polymerizing a monomer of the invention to form a basepolymer and (b) shaping the base polymer to form a shaped article.

In certain embodiments, the shaped article is an implantable medicaldevice, such as, without limitation, cardiac-assist devices, catheters,stents, prosthetic implants, artificial sphincters, or drug deliverydevices. In other embodiments the shaped article is a nonimplantablemedical device.

The polymerization step resulting in an oligofluorinated cross-linkedpolymer of the invention can be initiated, for example, using heat, UVradiation, a photoinitiator, or a free-radical initiator. Desirably, thepolymerization is initiated by heat.

In certain embodiments, the step of polymerizing further includes mixingthe monomer of the invention with a second compound containing a vinylgroup. The second compound can be another monomer of the invention or anonfluorinated vinyl compound, such as acrylic acid, methyl acrylate,ethyl acrylate, n-butyl acrylate, 2-hydroxyethyl acrylate, n-butylacrylate, glycidyl acrylate, vinyl acrylate, allyl acrylate,2-hydroxyethyl acrylate, 2-hydroxy ethyl methacrylate (HEMA), 2-aminoethyl methacrylate, glycerol monomethacrylate, acrylamide,methacrylamide, N-(3-aminopropyl) methacrylamide, crotonamide, allylalcohol, or 1,1,1-trimethylpropane monoallyl ether.

The invention also features a method for encapsulating a biologicallyactive agent in a polymer by (a) contacting a biologically active agentwith a monomer of the invention and (b) polymerizing the monomer to forman oligofluorinated cross-linked polymer.

The invention further features a composition including: (i) a firstcomponent having a core substituted with m nucleophilic groups, wherem≧2; and a second component having a core substituted with nelectrophilic groups, where m≧2 and m+n>4; wherein the compositionincludes at least one oligofluorinated nucleophilic group or oneoligofluorinated electrophilic group, and wherein the first componentand the second component react to form oligofluorinated cross-linkedpolymer.

In certain embodiments, the first component includes an oligomericsegment having a first end covalently tethered to a first nucleophilicgroup and a second end covalently tethered to a second nucleophilicgroup, wherein the first nucleophilic group or the second nucleophilicgroup is an oligofluorinated nucleophilic group. In other embodiments,the second component includes an oligomeric segment having a first endcovalently tethered to a first electrophilic group and a second endcovalently tethered to a second electrophilic group, wherein the firstelectrophilic group or the second electrophilic group is anoligofluorinated electrophilic group.

In still other embodiments, the first component or the second componentis further described by formula (V):

(G)-[(oligo)-(G)]_(n)   (V)

In formula (V) oligo is an oligomeric segment; G is either anucleophilic group or an electrophilic group; and n is an integer from 1to 5, wherein at least one G is an oligofluorinated nucleophilic groupor oligofluorinated electroophilic group.

In another embodiment, the first component or the second component isfurther described by formula (VI):

In formula (VI) oligo is an oligomeric segment; G is either anucleophilic group or an electrophilic group; F_(T) is an oligofluorogroup; each LinkA is, independently, an organic moiety covalently boundto oligo, F_(T), and G; and a, b, and c are integers greater than 0.

In the above aspect, the nucleophilic groups and the electrophilicgroups undergo a nucleophilic substitution reaction, a nucleophilicaddition reaction, or both upon mixing. The nucleophilic groups can beselected from, without limitation, primary amines, secondary amines,thiols, alcohols, and phenols. The electrophilic groups can be selectedfrom, without limitation, carboxylic acid esters, acid chloride groups,anhydrides, isocyanato, thioisocyanato, epoxides, activated hydroxylgroups, succinimidyl ester, sulfosuccinimidyl ester, maleimido, andethenesulfonyl. Desirably, the number of nucleophilic groups in themixture is approximately equal to the number of electrophilic groups inthe mixture (i.e., the ratio of moles of nucleophilic groups to moles ofelectrophilic groups is about 2:1 to 1:2, or even about 1:1).

In a related aspect, the invention features a method for coating asubstrate by (a) contacting the substrate with a composition of theinvention and (b) polymerizing the composition on the substrate to forma cross-linked coating.

The invention also features a method for making a shaped article by (a)polymerizing a composition of the invention to form a base polymer and(b) shaping the base polymer to form a shaped article.

In certain embodiments, the substrate is an implantable medical device,such as, without limitation, cardiac-assist devices, catheters, stents,prosthetic implants, artificial sphincters, or drug delivery devices. Inother embodiments the shaped article is a nonimplantable medical device.

In any of the above methods or compositions, the oligofluoro groups canbe selected from, without limitation, groups having the formula:

CF₃(CF₂)_(p)X, (CF₃)₂CF(CF₂)_(p)X, or (CF₃)₃C(CF₂)_(p)X,

wherein X is selected from CH₂CH₂—, (CH₂CH₂O)_(n), CH₂CH(OD)CH₂O—,CH₂CH(CH₂OD)O—, or D-; D is a moiety capable of chain growthpolymerization; p is an integer between 2 and 20; and n is an integerbetween 1 and 10.

In any of the above methods or compositions, the vinyl group can beselected, without limitation, from methylacrylate, acrylate, allyl,vinylpyrrolidone, and styrene derivatives.

In any of the above methods or compositions, the oligo can be selected,without limitation, from polyurethane, polyurea, polyamides,polyaklylene oxide, polycarbonate, polyester, polylactone, polysilicone,polyethersulfone, polypeptide, polysaccharide, polysiloxane,polydimethylsiloxane, polypropylene oxide, polyethylene oxide,polytetramethyleneoxide, and combinations thereof.

In any of the above methods or compositions, the biologically activeagent can be selected, without limitation, from proteins, peptides,carbohydrates, antibiotics, antiproliferative agents, rapamycinmacrolides, analgesics, anesthetics, antiangiogenic agents,antithrombotic agents, vasoactive agents, anticoagulants,immunomodulators, cytotoxic agents, antiviral agents, antibodies,neurotransmitters, psychoactive drugs, oligonucleotides, proteins,vitamins, lipids, and prodrugs thereof. The biologically active agentcan be any biologically active agent described herein.

The invention also features a method for coating a stent includinginitiating a polymerization reaction on the surface of the stent to forma polymerized coating. In certain embodiments, the polymerized coatingis a cross-linked polymer coating, such as an oligofluorinatedcross-linked polymer coating. The polymerization reaction can be, forexample, a chain growth polymerization reaction, a nucleophilicsubstitution reaction, or a nucleophilic addition reaction. In certainembodiments, the method includes (a) contacting the stent with a monomerof the invention or a composition of the invention; and (b) polymerizingthe monomer or polymerizing the composition to form a cross-linkedcoating.

In any of the above methods, an uncoated implantable medical device canbe coated to produce a coated implantable medical device, the coatedimplantable medical device having, upon implantation into an animal,reduced protein deposition, reduced fibrinogene deposition, reducedplatelet deposition, or reduced inflammatory cell adhesion in comparisonto the uncoated implantable medical device.

By “base polymer” is meant a polymer having a tensile strength of fromabout 350 to about 10,000 psi, elongation at break from about 5%, 25%,100%, or 300% to about 1500%, an unsupported thickness of from about 5to about 100 microns, and a supported thickness of from about 1 to about100 microns.

By “biologically active agent” is meant a compound, be itnaturally-occurring or artificially-derived, that is encapsulated in aoligofluorinated cross-linked polymer of the invention and which may bereleased and delivered to a specific site (e.g., the site at which amedical device is implanted). Biologically active agents may include,for example, peptides, proteins, synthetic organic molecules, naturallyoccurring organic molecules, nucleic acid molecules, and componentsthereof. Desirably, the biologically active agent is a compound usefulfor the therapeutic treatment of a plant or animal when delivered to asite of diseased tissue. Alternatively, the biologically active agentcan be selected to impart non-therapeutic functionality to a surface.Such agents include, for example, pesticides, bactericides, fungicides,fragrances, and dyes.

As used herein, “covalently tethered” refers to moieties separated byone or more covalent bonds. For example, where an oligofluoro group iscovalently tethered to a cross-linking domain, tethered includes themoieties separated by a single bond as well as both moieties separatedby, for example, a LinkA segment to which both moieties are covalentlyattached.

As used herein, “LinkA” refers to a coupling segment capable ofcovalently linking a cross-linking domain, an oligo segment, and anoligofluoro group. Typically, LinkA molecules have molecular weightsranging from 40 to 700. Preferably the LinkA molecules are selected fromthe group of functionalized diamines, diisocyanates, disulfonic acids,dicarboxylic acids, diacid chlorides and dialdehydes, wherein thefunctionalized component has secondary functional chemistry that isaccessed for chemical attachment of an oligofluoro group or a vinylgroup. Such secondary groups include, for example, esters, carboxylicacid salts, sulfonic acid salts, phosphonic acid salts, thiols, vinylsand secondary amines. Terminal hydroxyls, amines or carboxylic acids onthe oligo intermediates can react with diamines to form oligo-amides;react with diisocyanates to form oligo-urethanes, oligo-ureas,oligo-amides; react with disulfonic acids to form oligo-sulfonates,oligo-sulfonamides; react with dicarboxylic acids to form oligo-esters,oligo-amides; react with diacid chlorides to form oligo-esters,oligo-amides; and react with dialdehydes to form oligo-acetal oroligo-imines. It should be noted that in any of the above cases one ofthe functional groups of LinkA, e.g., primary groups of a diamine, couldbe substituted for another functional group such that the LinkA wouldbe, e.g., a hetero functional molecule (such as with an amine and acarboxylic acid as the primary groups) having a primary and a secondaryfunctional chemistry.

By “oligo” or “oligo segment” is meant a non-fluorinated relativelyshort length of a repeating unit or units, generally less than about 50monomeric units and molecular weights less than 10,000, but preferably<5000, and most preferably between 50 and 5,000 Daltons or between 100and 5,000 Daltons. Preferably, oligo is selected from the groupconsisting of polyurethane, polyurea, polyamides, polyalkylene oxide,polycarbonate, polyester, polylactone, polysilicone, polyethersulfone,polyolefin, polyvinyl, polypeptide, polysaccharide; and ether and aminelinked segments thereof. Alternatively, the oligo segment is as small asethylenediamine.

By “oligofluorinated nucleophilic group” is meant a nucleophilecovalently tethered to an oligofluoro group and separated by fewer than25, 22, 18, or even 15 covalent bonds. Nucleophiles that can be used inthe methods and compositions of the invention include, withoutlimitation, amines, and thiols.

By “oligofluorinated electrophilic group” is meant an electrophilecovalently tethered to an oligofluoro group and separated by fewer than25, 22, 18, or even 15 covalent bonds. Electrophiles that can be used inthe methods and compositions of the invention include, withoutlimitation, activated acids, epoxy groups, and isocyanates.

By “oligofluorinated cross-linking domain” is meant a cross-linkingdomain covalently tethered to an oligofluoro group and separated byfewer than 25, 22, 18, or even 15 covalent bonds. The oligofluorinatedcross-linked polymers of the invention can be formed from a monomerwhich contains at least one oligofluorinated cross-linking domain.

By “oligofluorinated cross-linked polymer” is meant a cross-linkedpolymer including an oligomeric segment and pendant oligofluoro groups.

By “cross-linking domain” is meant a moiety capable of forming covalentlinkages via chain growth polymerization reactions. Chain growthpolymerization reactions are reactions in which unsaturated monomermolecules add on to a growing polymer chain one at a time, as providedin the following equation:

Cross-linking domains can be designed to undergo radical initiated chainpolymerization (i.e., in the polymerization of vinyl groups to producepolyvinyl), cationic chain growth polymerization reactions (i.e.,cationic ring-opening polymerization, such as in the polymerization ofepoxides to produce polyethers, and oxazolines to produce acylatedpolyamines), and anionic chain growth polymerization reactions (i.e.,anionic ring-opening polymerization, such as in the polymerization ofepoxides to produce polyethers, and N-methanesulfonyl-2-methylaziridineto produce polyamines).

By “vinyl monomer” is meant an oligo segment covalently tethered to twoor more vinyl groups capable of undergoing radical initiatedpolymerization, wherein at least one vinyl group is contained within anoligofluorinated cross-linking domain.

Other features and advantages of the invention will be apparent from thefollowing Detailed Description, the Drawings, and the Claims.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is an image of a UV cured film of Compound 2, with tensiletesting articles punched out, showing Compound 2 processing capability.

FIG. 2 is an image of a heat cured film of Compound 2, demonstratingCompound 2 processing capability.

FIG. 3 is an image of heat cured shaped articles of Compound 2, showinghow an article can be made from Compound 2.

FIG. 4 is an image of a heat cured film of Compound 6, demonstratingCompound 6 processing capability.

FIG. 5 is two SEM images of heat cured films of Compound 6, before andafter toluene extraction, showing the final product properties to remainintact.

FIG. 6 is an image of a heat cured film of Compound 12, demonstratingCompound 12 processing capability.

FIG. 7 is an image of a heat cured film of Compound 2 and Compound 6,showing Compound 2 and Compound 6 processing capability.

FIG. 8 is an image of a heat cured film of Compound 6 and Compound 8,showing Compound 6 and Compound 8 processing capability.

FIG. 9 is an image of a heat cured film of Compound 6 and FEO1,demonstrating Compound 6 processing capability.

FIG. 10 is an image of a heat cured film of Compound 6 and HEMA, showingCompound 6 processing capability.

FIG. 11 is an image of a stent coated with heat cured Compound 2,showing good coverage with minimal webbing.

FIG. 12 is an image of an air-deployed stent, coated with heat curedCompound 2, showing good coverage with minimal webbing.

FIG. 13 is an image of a stent coated with heat cured Compound 6,demonstrating good coverage with minimal webbing.

FIG. 14 is an image of a stent coated with heat cured Compound 6,extracted with toluene, demonstrating the final product properties toremain intact.

FIG. 15 is an image of a stent coated with heat cured Compound 6,extracted with buffer, showing the final product properties to remainintact.

FIG. 16 is an image of a stent coated with heat cured Compound 8,demonstrating good coverage with minimal webbing.

FIG. 17 is an image of a stent coated with heat cured Compound 12(toluene solvent), showing good coverage with minimal webbing.

FIG. 18 is an image of a stent coated with heat cured Compound 12(toluene:THF solvent), showing good coverage with minimal webbing.

FIG. 19 is an image of a stent coated with heat cured Compound 2 andCompound 6, showing good coverage with minimal webbing.

FIG. 20 is an image of a stent coated with heat cured Compound 6 andCompound 8, showing good coverage with minimal webbing.

FIG. 21 is an image of a stent coated with heat cured Compound 6 andPTX, showing good coverage with minimal webbing.

FIG. 22 is a plot of ASA release from a UV cured film of Compound 2 with10 wt % ASA, showing the release of ASA from Compound 2.

FIG. 23 is a plot of ASA release from a UV cured film of Compound 2 with25 wt % ASA, showing the ability of ASA to be released from Compound 2.

FIG. 24 is a plot of ibuprofen release from a heat cured film ofCompound 2, demonstrating the ability of ibuprofen to be released fromCompound 2.

FIG. 25 is a plot of hydrocortisone and dexamethasone release from heatcured films of Compound 6, demonstrating the ability to release drugsfrom Compound 6.

FIG. 26 is an image of a stent coated with heat cured Compound 6 with 1wt % hydrocortisone, showing good coverage.

FIG. 27 is a plot of U937 adhesion to cured films of Compounds 2, 6, 8,and 12, cast on PP, demonstrating a significant reduction in celladhesion profile.

FIG. 28 is is a plot of U937 adhesion to cured films of Compounds 2, 6,8, and 12, cast on stainless steel, demonstrating a substantialreduction in cell adhesion profile.

FIG. 29 is a plot of platelet and fibrinogen interaction with curedfilms of Compounds 2 and 6, showing a significant reduction in plateletadhesion and fibrinogen adsorption.

DETAILED DESCRIPTION

The invention features oligofluorinated cross-linked polymers. Oncecured, the oligofluorinated cross-linked polymer is useful as a basepolymer in the manufacture of articles or as an oligofluorinatedcoating. In certain embodiments, the oligofluorinated cross-linkedpolymer is formed from a combination of both chain growth and stepgrowth polymerization reactions. The coatings of the invention can alsobe used to encapsulate therapeutic agents.

The oligofluorinated cross-linked polymers of the invention can beproduced via chain growth polymerization reactions, nucleophilicsubstitution reactions, and/or a nucleophilic addition reactions.Regardless of how the oligofluorinated cross-linked polymer is produced,the resulting polymer will include pendant oligofluoro groups, anoligomeric segment, and, optionally, LinkA groups (used to covalentlytether the various components together).

The quality and performance of the oligofluorinated cross-linkedpolymers can be varied depending upon the chemical composition and curedcharacteristics of polymerization step. Desirably, the precursormonomers materials exhibit high reactivity, resulting in efficientcuring and fast curing kinetics. The oligofluorinated cross-linkedpolymers of the invention can be designed to result in a wide variety ofdesired mechanical properties, release profiles (where a biologicallyactive agent is incorporated), and reduced protein and cell interactions(e.g., when used for in vivo applications). In part, this task entailsand defines the formation of a three dimensional network. As shown inthe examples, the properties can vary with chemical composition of theoligofluorinated precursor (e.g., altering the oligo segment or thepositioning of the cross linking domain within) and with thepolymerization conditions (e.g., by the inclusion of additives, oraltering the concentration of the oligofluorinated precursor, to alterthe cross-linking density). The extent to which the properties of theoligofluorinated cross-linked polymer can be controlled is one of theadvantages of the invention.

Oligofluoro Groups

The monomers of the invention include at least one oligofluoro group.Typically, the oligofluoro group (F_(T)) has a molecular weight rangingfrom 100 to 1,500 and is incorporated into the oligomers of theinvention by reaction of the corresponding perfluoroalkyl group withLinkA moiety. Desirably, F_(T) is selected from a group consisting ofradicals of the general formula: CF₃(CF₂)_(p)CH₂CH₂,(CF₃)₂CF(CF₂)_(p)CH₂CH₂, or (CF₃)₃C(CF₂)_(p)CH₂CH₂, wherein p is 2-20,preferably 2-8, and CF₃(CF₂)_(m)(CH₂CH₂O)_(n),(CF₃)₂CF(CF₂)_(m)(CH₂CH₂O)_(n), or (CF₃)₃C(CF₂)_(m)(CH₂CH₂O)_(n),wherein n is 1-10 and m is 1-20, preferably 1-8. F_(T) can beincorporated into a monomer by reaction of an oligofluorinated alcoholwith LinkA or an oligo segment. F_(T) typically includes a singlefluoro-tail, but are not limited to this feature. A general formula forthe oligomeric fluoro-alcohol of use in the invention isH—(OCH₂CH₂)_(n)—(CF₂)_(m)—CF₃, wherein n can range from 1 to 10, butpreferably ranges from 1 to 4, and m can range from 1 to 20, butpreferably ranges from 1-8. A general guide for the selection of nrelative to m is that m should be equal to or greater than 2n in orderto minimize the likelihood of the (OCH₂CH₂)_(n) segment displacing the(CF₂)_(m)—CF₃ from the surface following exposure to water, since theformer is more hydrophilic than the fluoro-tail and will compete withthe fluoro-tail for surface dominance in the polymerized form. Thepresence of the (OCH₂CH₂)_(n) segment is believed to have an importantfunction within the oligofluoro domain, as it provides a highly mobilespacer segment between the fluoro-tail and the substrate. This spacereffectively exposes the oligofluorinated surface to, for example, anaqueous medium.

Examples of oligofluoro groups that incorporate reactive moieties forundergoing cross-linking are provided in Table 1. The examples providedinclude vinyl groups for undergoing chain growth polymerizations.Similar oligofluoro groups incorporating nucleophiles or electrophilescan be prepared for use in the preparation of oligofluorinatedcross-linked polymers made via nucleophilic substitution reactions,and/or a nucleophilic addition reactions.

TABLE 1

Perfluoro-2-hydroxy acrylates (generic class, various perfluoro) (FEO1)

Perfluoro-2-hydroxy- trifluoromethyl acrylates (generic class, variousperfluoro)

Perfluoro-2-hydroxy methacrylates (generic class, various perfluoro)

Perfluoro-2-hydroxy- trifluoromethyl methacrylates (generic class,various perfluoro) (FEO3)

Perfluoren-1-ol (generic class, various perfluoro) (FEO2)

Perfluoren-1-ol with longer CH₂ chains (generic class, variousperfluoro)

Oligomeric Segment

The monomers of the invention include at least one oligomeric segment.The oligo segment is covalently tethered to two or more cross-linkingdomains and at least one oligofluoro group. Oligo segments can include,for example, polytetramethylene oxide, polycarbonate, polysiloxane,polypropylene oxide, polyethylene oxide, polyamide, polysaccharide, orany other oligomeric chain. The oligo segment can include two or morehydroxyls, thiols, carboxylic acids, diacid chlorides or amides forcoupling with LinkA, a cross-linking domain, and/or an oligofluorogroup. Useful oligo segments include, without limitation, linear diamineor diol derivatives of polycarbonate, polysiloxanes,polydimethylsiloxanes; polyethylene-butylene co-polymers;polybutadienes; polyesters; polyurethane/sulfone co-polymers;polyurethanes, polyamides including oligopeptides (polyalanine,polyglycine or copolymers of amino-acids) and polyureas; polyalkyleneoxides and specifically polypropylene oxide, polyethylene oxide andpolytetramethylene oxide. The average molecular weight of the oligosegment can vary from 50 to 5,000 or 100 to 5,000, but in certainembodiments is less than 2,500 Daltons. Oligomeric components can berelatively short in length in terms of the repeating unit or units, andare generally less than 20 monomeric units.

LinkA

The monomers of the invention optionally include one or more LinkAgroups. Typically, LinkA groups have molecular weights ranging from 40to 700 Da and have multiple functionality in order to permit coupling ofoligo segments, F_(T), and/or cross-linking domains. Examples of LinkAgroups include, without limitation, lysine diisocyanato esters (e.g.,lysine diisocyanato methyl ester); 2,5-diaminobenzenesulfonic acid;4,4′diamino 2,2′-biphenyl disulfonic acid; 1,3-diamino 2-hydroxypropane;and N-(2-aminoethyl)-3-aminopropane sulfonate.

Cross-Linking Domains

Cross-linking domains can be selected from a variety of differentmoieties which can undergo chain growth polymerizations. For example,cross-linking domains can be designed to undergo radical initiated chainpolymerization (i.e., in the polymerization of vinyl groups to producepolyvinyl), cationic chain growth polymerization reactions (i.e.,cationic ring-opening polymerization, such as in the polymerization ofepoxides to produce polyethers, and oxazolines to produce acylatedpolyamines), and anionic chain growth polymerization reactions (i.e.,anionic ring-opening polymerization, such as in the polymerization ofepoxides to produce polyethers, and N-methanesulfonyl-2-methylaziridineto produce polyamines). Many different chain growth polymerizationapproaches are known in the art and can be included in the methods andcompositions of the invention.

The oligofluorinated cross-linked polymers of the invention can beformed from a monomer which contains at least one oligofluorinatedcross-linking domain. For example, such monomers can include at leastone pendant oligofluoro chain (F_(T)) located adjacent to a step growthresultant functional group (urethane, urea, amide, ester, etc.) withinLinkA, or an oligo segment, and at least two unreacted pendantcross-linking domains. The cross-linking domains and F_(T) can becovalently tethered to a non-fluorinated oligo segment via LinkA, orF_(T) can be directly tethered to a cross-linking domain and, together,covalently linked to the oligo segment via LinkA. Both LinkA and theoligo segment may designed to provide for a defined spatial distributionof F_(T) groups, where more than one F_(T) group is present in themonomer. This distribution simultaneously serves as a definingparameter, dictating the modulus, protein and cell interactions, andbiochemical stability of the final polymer.

In certain embodiments, the monomer of the invention includes at leasttwo vinyl groups. The vinyl groups are derivatized to include at leastone functional group (e.g., a carboxylic acid, hydroxyl, amine, or thiolgroup), which is used to covalently tether the vinyl group to abiologically active agent, LinkA, and/or oligo. Vinyl groups useful inthe methods and compositions of the invention include, withoutlimitation, methacrylate, acrylate, cyclic or linear vinyl moieties, andallyl and styrene containing moieties, and typically have molecularweights ranging from 40 to 2000.

Oligofluorinated Nucleophilic and Electrophilic Groups

In invention provides a composition is provided that contains at leasttwo components having reactive groups thereon, with the functionalgroups selected so as to enable reaction between the components, i.e.,crosslinking to form an oligofluorinated cross-linked polymer. Eachcomponent has a core substituted with reactive groups. Typically, thecomposition will contain a first component having a core substitutedwith nucleophilic groups and a second component having a coresubstituted with electrophilic groups. The composition includes at leastone oligofluorinated nucleophilic group or at least one oligofluorinatedelectrophilic group.

In order for a cross-linked polymer to be formed, there is preferablyplurality of reactive groups present in each of the first and secondcomponents. For example, one component may have a core substituted withm nucleophilic groups, where m≧2, and the other component has a coresubstituted with n electrophilic groups, where n≧2 and m+n>4.

The reactive groups are electrophilic and nucleophilic groups, whichundergo a nucleophilic substitution reaction, a nucleophilic additionreaction, or both. The term “electrophilic” refers to a reactive groupthat is susceptible to nucleophilic attack, i.e., susceptible toreaction with an incoming nucleophilic group. Electrophilic groupsherein are positively charged or electron-deficient, typicallyelectron-deficient. The term “nucleophilic” refers to a reactive groupthat is electron rich, has an unshared pair of electrons acting as areactive site, and reacts with a positively charged orelectron-deficient site.

Examples of nucleophilic groups suitable for use in the inventioninclude, without limitation, primary amines, secondary amines, thiols,phenols, and alcohols. Certain nucleophilic groups must be activatedwith a base so as to be capable of reaction with an electrophilic group.For example, when there are nucleophilic sulfhydryl and hydroxyl groupsin the multifunctional compound, the compound must be admixed with anaqueous base in order to remove a proton and provide a thiolate orhydroxylate anion to enable reaction with the electrophilic group.Unless it is desirable for the base to participate in the reaction, anon-nucleophilic base is preferred. In some embodiments, the base may bepresent as a component of a buffer solution.

The selection of electrophilic groups provided on the multifunctionalcompound, must be made so that reaction is possible with the specificnucleophilic groups. Thus, when the X reactive groups are amino groups,the Y groups are selected so as to react with amino groups. Analogously,when the X reactive groups are sulfhydryl moieties, the correspondingelectrophilic groups are sulfhydryl-reactive groups, and the like.Examples of electrophilic groups suitable for use in the inventioninclude, without limitation, carboxylic acid esters, acid chloridegroups, anhydrides, isocyanato, thioisocyanato, epoxides, activatedhydroxyl groups, succinimidyl ester, sulfosuccinimidyl ester, maleimido,and ethenesulfonyl. Carboxylic acid groups typically must be activatedso as to be reactive with a nucleophile. Activation may be accomplishedin a variety of ways, but often involves reaction with a suitablehydroxyl-containing compound in the presence of a dehydrating agent suchas dicyclohexylcarbodiimide (DCC) or dicyclohexylurea (DHU). Forexample, a carboxylic acid can be reacted with an alkoxy-substitutedN-hydroxy-succinimide or N-hydroxysulfosuccinimide in the presence ofDCC to form reactive electrophilic groups, the N-hydroxysuccinimideester and the N-hydroxysulfosuccinimide ester, respectively. Carboxylicacids may also be activated by reaction with an acyl halide such as anacyl chloride (e.g., acetyl chloride), to provide a reactive anhydridegroup. In a further example, a carboxylic acid may be converted to anacid chloride group using, e.g., thionyl chloride or an acyl chloridecapable of an exchange reaction.

In general, the concentration of each of the components will be in therange of about 1 to 50 wt %, generally about 2 to 40 wt %. The preferredconcentration will depend on a number of factors, including the type ofcomponent (i.e., type of molecular core and reactive groups), itsmolecular weight, and the end use of the resulting three-dimensionalmatrix. For example, use of higher concentrations of the components, orusing highly functionalized components, will result in the formation ofa more tightly crosslinked network, producing a stiffer, more robustcomposition, such as for example a gel. In general, the mechanicalproperties of the three-dimensional matrix should be similar to themechanical properties of the surface to which the matrix (ormatrix-forming components) will be applied. Thus, when the matrix willbe used for an orthopedic application, the gel matrix should berelatively firm, e.g., a firm gel; however, when the matrix will be usedon soft tissue, as for example in tissue augmentation, the gel matrixshould be relatively soft, e.g., a soft gel.

Further details of the formation of oligofluorinated cross-linkedpolymers is provided in the Examples.

Substrates which can be coated using the methods and compositions of theinvention include, without limitation, wood, metals, ceramics, plastics,stainless steels, fibers, and glasses, among others.

Synthesis

The oligofluorinated cross-linked polymers of the invention aresynthesized from monomers which can be prepared, for example, asdescribed in Schemes 1-4 below. In Schemes 1-4, oligo is an oligomericsegment, LinkA is a linking element as defined herein, Bio is abiologically active agent, F_(T) is an oligofluoro group, and D is amoiety capable of undergoing a chain growth polymerization reaction,nucleophilic substitution reaction, and/or a nucleophilic additionreaction.

The monomers can be synthesized, for example, using multi-functionalLinkA groups, a multi-functional oligo segment, a mono-functional F_(T)group, and cross-linking domains having at least one functionalcomponent that can be covalently tethered to the oligomeric segment.

The first step of the synthesis can be carried out by classicalurethane/urea reactions using the desired combination of reagents.However, the order in which the various components are assembled can bevaried for any particular monomer.

Further synthetic details are provided in the Examples.

Oligofluorinated Cross-Linked Polymerized Coatings

The oligofluorinated cross-linked polymers of the invention can be usedto form coatings which provide for the discrete distribution ofmono-dispersed oligofluoro groups in a pendant arrangement on a surfacethat is stable (e.g., does not readily leach from the surface).

The coatings of the invention can be formed by polymerization of anoligofluorinated cross-linking domain, such as a vinyl monomer, or byreaction of a multifunctional nucleophile with an oligofluorinatedelectrophile or a multifunctional electrophile with an oligofluorinatednucleophile.

The coatings of the invention can impart high water repellency, lowrefractive index, soil resistance, reduce fouling, and improvebiocompatibility. For blood dwelling devices the coatings can reduce theformation of blood clots at the device surface after implantation.

The monomer can be applied to a surface alone (e.g., as a liquid); inthe presence of a diluent (e.g., acetone, methanol, ethanol, ethers,hexane, toluene, or tetrahydrofuran), in combination with anoligofluorinated precursor. Suitable methods for applying the monomer toa surface include, without limitation, spin coating, spraying, rollcoating, dipping, brushing, and knife coating, among others.

Polymerization of the monomers of the invention can be achieved by UVradiation, electron beam, or thermal heat in the presence of aphotoinitiator or free-radical thermal initiator, depending upon thenature of the reactive moiety employed. Many light energy sources can beused and a typical source is ultraviolet (UV) radiation. A typical UVlamp is a lamp equipped with a lamp output of 400 W/in (purchased fromHonle UV America Inc.). The lamp is secured on top of a home-built box(26.5 cm length, 26.5 cm width and 23.0 cm height). The box is designedto control the curing environment, using either an air or nitrogenatmosphere.

A wide variety of articles can be coated using the compositions andmethods of the invention. For example, articles which contact bodilyfluids, such as medical devices can be coated to improve theirbiocompatibility. The medical devices include, without limitation,catheters, guide wires, vascular stents, micro-particles, electronicleads, probes, sensors, drug depots, transdermal patches, vascularpatches, blood bags, and tubing. The medical device can be an implanteddevice, percutaneous device, or cutaneous device. Implanted devicesinclude articles that are fully implanted in a patient, i.e., arecompletely internal. Percutaneous devices include items that penetratethe skin, thereby extending from outside the body into the body.Cutaneous devices are used superficially. Implanted devices include,without limitation, prostheses such as pacemakers, electrical leads suchas pacing leads, defibrillarors, artificial hearts, ventricular assistdevices, anatomical reconstruction prostheses such as breast implants,artificial heart valves, heart valve stents, pericardial patches,surgical patches, coronary stents, vascular grafts, vascular andstructural stents, vascular or cardiovascular shunts, biologicalconduits, pledges, sutures, annuloplasty rings, stents, staples, valvedgrafts, dermal grafts for wound healing, orthopedic spinal implants,orthopedic pins, intrauterine devices, urinary stents, maxial facialreconstruction plating, dental implants, intraocular lenses, clips,sternal wires, bone, skin, ligaments, tendons, and combination thereof.Percutaneous devices include, without limitation, catheters or varioustypes, cannulas, drainage tubes such as chest tubes, surgicalinstruments such as forceps, retractors, needles, and gloves, andcatheter cuffs. Cutaneous devices include, without limitation, burndressings, wound dressings and dental hardware, such as bridge supportsand bracing components.

The coating of an implantable medical device such as a vascular stent isof great interest. Stents are commonly used for the treatment ofstenosis. Generally, stent is crimped onto a balloon catheter, insertedin the coronary vessel of blockage and the balloon is inflated causingthe stent to expand to a desired diameter hence opening up the blockedartery vessel for blood flow. However, during this deployment process,damages to the artery wall can cause elastic recoil of the vessel wallwhich characterizes the early phase of restenosis. Stent coating offersa platform for the delivery of biologically active agents for controlingpost deployment restenosis. Using the methods and compositions of theinvention, drug delivery on the stent is achieved by formulating asolution with a polymer dissolved in a solvent, and a biologicallyactive agent dispersed in the blend. When the solution is sprayed on thestent, the solvent is allowed to evaporate, leaving on the stent surfacethe polymer with the drug embedded in the polymer matrix. Alternatively,the biologically active agent is covalently bound to theoligofluorinated precursor prior to polymerization. The release of thebiologically active agent covalently bound to the resultingoligofluorinated cross-linked polymer can be controlled by utilizing adegradable linker (e.g., a ester linkage) to attach the biologicallyactive agent.

Alternatively, the coatings of the invention can be applied to wood forexterior applications (decks and fences), boats, ships, fabrics,electronic displays, gloves, and apparel.

One distinctive feature of the intercalative oligofluorinatedcross-linked polymer is the ability to initiate the polymerization stepon the device surface, producing a continuous polymer coating similar toskin wrap.

Shaped Articles

Articles can be formed from the oligofluorinated cross-linked polymersof the invention. For example, the oligofluorinated precursor can becombined with an initiator using reaction injection molding to produce ashaped article.

Any shaped article can be made using the compositions of the invention.For example, articles suitable for contact with bodily fluids, such asmedical devices can be made using the compositions described herein. Theduration of contact may be short, for example, as with surgicalinstruments or long term use articles such as implants. The medicaldevices include, without limitation, catheters, guide wires, vascularstents, micro-particles, electronic leads, probes, sensors, drug depots,transdermal patches, vascular patches, blood bags, and tubing. Themedical device can be an implanted device, percutaneous device, orcutaneous device. Implanted devices include articles that are fullyimplanted in a patient, i.e., are completely internal. Percutaneousdevices include items that penetrate the skin, thereby extending fromoutside the body into the body. Cutaneous devices are usedsuperficially. Implanted devices include, without limitation, prosthesessuch as pacemakers, electrical leads such as pacing leads,defibrillarors, artificial hearts, ventricular assist devices,anatomical reconstruction prostheses such as breast implants, artificialheart valves, heart valve stents, pericardial patches, surgical patches,coronary stents, vascular grafts, vascular and structural stents,vascular or cardiovascular shunts, biological conduits, pledges,sutures, annuloplasty rings, stents, staples, valved grafts, dermalgrafts for wound healing, orthopedic spinal implants, orthopedic pins,intrauterine devices, urinary stents, maxial facial reconstructionplating, dental implants, intraocular lenses, clips, sternal wires,bone, skin, ligaments, tendons, and combination thereof. Percutaneousdevices include, without limitation, catheters or various types,cannulas, drainage tubes such as chest tubes, surgical instruments suchas forceps, retractors, needles, and gloves, and catheter cuffs.Cutaneous devices include, without limitation, burn dressings, wounddressings and dental hardware, such as bridge supports and bracingcomponents.

Biologically Active Agents

Biologically active agents can be encapsulated within the coatings andarticles of the invention. The encapsulation can be achieved either bycoating the article to be treated with a biologically active agent priorto application and polymerization of the monomer, or by mixing themonomer and the biologically active agent together and applying themixture to the surface of the article prior to polymerization.Biologically active agents include therapeutic, diagnostic, andprophylactic agents. They can be naturally occurring compounds,synthetic organic compounds, or inorganic compounds. Biologically activeagents that can be used in the methods and compositions of the inventioninclude, but are not limited to, proteins, peptides, carbohydrates,antibiotics, antiproliferative agents, rapamycin macrolides, analgesics,anesthetics, antiangiogenic agents, vasoactive agents, anticoagulants,immunomodulators, cytotoxic agents, antiviral agents, antithromboticdrugs, such as terbrogrel and ramatroban, antibodies, neurotransmitters,psychoactive drugs, oligonucleotides, proteins, lipids, and anybiologically active agent described herein.

Exemplary therapeutic agents include growth hormone, for example humangrowth hormone, calcitonin, granulocyte macrophage colony stimulatingfactor (GMCSF), ciliary neurotrophic factor, and parathyroid hormone.Other specific therapeutic agents include parathyroid hormone-relatedpeptide, somatostatin, testosterone, progesterone, estradiol, nicotine,fentanyl, norethisterone, clonidine, scopolomine, salicylate,salmeterol, formeterol, albeterol, valium, heparin, dermatan,ferrochrome A, erythropoetins, diethylstilbestrol, lupron, estrogenestradiol, androgen halotestin, 6-thioguanine, 6-mercaptopurine,zolodex, taxol, lisinopril/zestril, streptokinase, aminobutytric acid,hemostatic aminocaproic acid, parlodel, tacrine, potaba, adipex,memboral, phenobarbital, insulin, gamma globulin, azathioprine, papein,acetaminophen, ibuprofen, acetylsalicylic acid, epinephrine,flucloronide, oxycodone percoset, dalgan, phreniline butabital,procaine, novocain, morphine, oxycodone, aloxiprin, brofenac,ketoprofen, ketorolac, hemin, vitamin B-12, folic acid, magnesium salts,vitamine D, vitamin C, vitamin E, vitamin A, Vitamin U, vitamin L,vitamin K, pantothenic acid, aminophenylbutyric acid, penicillin,acyclovir, oflaxacin, amoxicillin, tobramycin, retrovior, epivir,nevirapine, gentamycin, duracef, ablecet, butoxycaine, benoxinate,tropenzile, diponium salts, butaverine, apoatropine, feclemine,leiopyrrole, octamylamine, oxybutynin, albuterol, metaproterenol,beclomethasone dipropionate, triamcinolone acetamide, budesonideacetonide, ipratropium bromide, flunisolide, cromolyn sodium, ergotaminetartrate, and protein or peptide drugs such as TNF antagonists orinterleukin antagonists. For example, the biologically active agent canbe an antiinflammatory agent, such as an NSAID, corticosteriod, or COX-2inhibitor, e.g., rofecoxib, celecoxib, valdecoxib, or lumiracoxib.

Exemplary diagnostic agents include imaging agents, such as those thatare used in positron emission tomography (PET), computer assistedtomography (CAT), single photon emission computerized tomography, X-ray,fluoroscopy, and magnetic resonance imaging (MRI). Suitable materialsfor use as contrast agents in MRI include gadolinium chelates, as wellas iron, magnesium, manganese, copper, and chromium chelates. Examplesof materials useful for CAT and X-rays include iodine based materials.

A preferred biologically active agent is a substantially purifiedpeptide or protein. Proteins are generally defined as consisting of 100amino acid residues or more; peptides are less than 100 amino acidresidues. Unless otherwise stated, the term protein, as used herein,refers to both proteins and peptides. The proteins may be produced, forexample, by isolation from natural sources, recombinantly, or throughpeptide synthesis. Examples include growth hormones, such as humangrowth hormone and bovine growth hormone; enzymes, such as DNase,proteases, urate oxidase, alronidase, alpha galactosidase, and alphaglucosidase; antibodies, such as trastuzumab.

Rapamycin Macrolides

Rapamycin (Sirolimus) is an immunosuppressive lactam macrolide that isproduced by Streptomyces hygroscopicus. See, for example, McAlpine, J.B., et al., J. Antibiotics 44: 688 (1991); Schreiber, S. L., et al., J.Am. Chem. Soc. 113: 7433 (1991); and U.S. Pat. No. 3,929,992,incorporated herein by reference. Exemplary rapamycin macrolides whichcan be used in the methods and compositions of the invention include,without limitation, rapamycin, CCI-779, Everolimus (also known asRAD001), and ABT-578. CCI-779 is an ester of rapamycin (42-ester with3-hydroxy-2-hydroxymethyl-2-methylpropionic acid), disclosed in U.S.Pat. No. 5,362,718. Everolimus is an alkylated rapamycin(40-O-(2-hydroxyethyl)-rapamycin, disclosed in U.S. Pat. No. 5,665,772.

Antiproliferative Agents

Exemplary antiproliferative agents which can be used in the methods andcompositions of the invention include, without limitation,mechlorethamine, cyclophosphamide, iosfamide, melphalan, chlorambucil,uracil mustard, estramustine, mitomycin C, AZQ, thiotepa, busulfan,hepsulfam, carmustine, lomustine, semustine, streptozocin, dacarbazine,cisplatin, carboplatin, procarbazine, methotrexate, trimetrexate,fluouracil, floxuridine, cytarabine, fludarabine, capecitabine,azacitidine, thioguanine, mercaptopurine, allopurine, cladribine,gemcitabine, pentostatin, vinblastine, vincristine, etoposide,teniposide, topotecan, irinotecan, camptothecin, 9-aminocamptothecin,paclitaxel, docetaxel, daunorubicin, doxorubicin, dactinomycin,idarubincin, plicamycin, mitomycin, amsacrine, bleomycin,aminoglutethimide, anastrozole, finasteride, ketoconazole, tamoxifen,flutamide, leuprolide, goserelin, Gleevec™ (Novartis), leflunomide(Pharmacia), SU5416 (Pharmacia), SU6668 (Pharmacia), PTK787 (Novartis),Iressa™ (AstraZeneca), Tarceva™, (Oncogene Science), trastuzumab(Genentech), Erbitux™ (ImClone), PKI166 (Novartis), GW2016(GlaxoSmithKline), EKB-509 (Wyeth), EKB-569 (Wyeth), MDX-H210 (Medarex),2C4 (Genentech), MDX-447 (Medarex), ABX-EGF (Abgenix), CI-1033 (Pfizer),Avastin™ (Genentech), IMC-1C11 (ImClone), ZD4190 (AstraZeneca), ZD6474(AstraZeneca), CEP-701 (Cephalon), CEP-751 (Cephalon), MLN518(Millenium), PKC412 (Novartis), 13-cis-retinoic acid, isotretinoin,retinyl palmitate, 4-(hydroxycarbophenyl)retinamide, misonidazole,nitracrine, mitoxantrone, hydroxyurea, L-asparaginase, interferon alfa,AP23573, Cerivastatin, Troglitazone, CRx-026DHA-paclitaxel, Taxoprexin,TPI-287, Sphingosine-based lipids, and mitotane.

Corticosteroids

Exemplary corticosteroids which can be used in the methods andcompositions of the invention include, without limitation,21-acetoxypregnenolone, alclomerasone, algestone, amcinonide,beclomethasone, betamethasone, betamethasone valerate, budesonide,chloroprednisone, clobetasol, clobetasol propionate, clobetasone,clobetasone butyrate, clocortolone, cloprednol, corticosterone,cortisone, cortivazol, deflazacon, desonide, desoximerasone,dexamethasone, diflorasone, diflucortolone, difluprednate, enoxolone,fluazacort, flucloronide, flumethasone, flumethasone pivalate,flunisolide, flucinolone acetonide, fluocinonide, fluorocinoloneacetonide, fluocortin butyl, fluocortolone, fluorocortolone hexanoate,diflucortolone valerate, fluorometholone, fluperolone acetate,fluprednidene acetate, fluprednisolone, flurandenolide, formocortal,halcinonide, halometasone, halopredone acetate, hydrocortamate,hydrocortisone, hydrocortisone acetate, hydrocortisone butyrate,hydrocortisone phosphate, hydrocortisone 21-sodium succinate,hydrocortisone tebutate, mazipredone, medrysone, meprednisone,methylprednicolone, mometasone furoate, paramethasone, prednicarbate,prednisolone, prednisolone 21-diedryaminoacetate, prednisolone sodiumphosphate, prednisolone sodium succinate, prednisolone sodium21-m-sulfobenzoate, prednisolone sodium 21-stearoglycolate, prednisolonetebutate, prednisolone 21-trimethylacetate, prednisone, prednival,prednylidene, prednylidene 21-diethylaminoacetate, tixocortol,triamcinolone, triamcinolone acetonide, triamcinolone benetonide andtriamcinolone hexacetonide. Structurally related corticosteroids havingsimilar anti-inflammatory properties are also intended to be encompassedby this group.

NSAIDs

Exemplary non-steroidal antiinflammatory drugs (NSAIDs) which can beused in the methods and compositions of the invention include, withoutlimitation, naproxen sodium, diclofenac sodium, diclofenac potassium,aspirin, sulindac, diflunisal, piroxicam, indomethacin, ibuprofen,nabumetone, choline magnesium trisalicylate, sodium salicylate,salicylsalicylic acid (salsalate), fenoprofen, flurbiprofen, ketoprofen,meclofenamate sodium, meloxicam, oxaprozin, sulindac, and tolmetin.

Analgesics

Exemplary analgesics which can be used in the methods and compositionsof the invention include, without limitation, morphine, codeine, heroin,ethylmorphine, O-carboxymethylmorphine, O-acetylmorphine, hydrocodone,hydromorphone, oxymorphone, oxycodone, dihydrocodeine, thebaine,metopon, ethorphine, acetorphine, diprenorphine, buprenorphine,phenomorphan, levorphanol, ethoheptazine, ketobemidone, dihydroetorphineand dihydroacetorphine.

Antimicrobials

Exemplary antimicrobials which can be used in the methods andcompositions of the invention include, without limitation, penicillin G,penicillin V, methicillin, oxacillin, cloxacillin, dicloxacillin,nafcillin, ampicillin, amoxicillin, carbenicillin, ticarcillin,mezlocillin, piperacillin, azlocillin, temocillin, cepalothin,cephapirin, cephradine, cephaloridine, cefazolin, cefamandole,cefuroxime, cephalexin, cefprozil, cefaclor, loracarbef, cefoxitin,cefmatozole, cefotaxime, ceftizoxime, ceftriaxone, cefoperazone,ceftazidime, cefixime, cefpodoxime, ceftibuten, cefdinir, cefpirome,cefepime, BAL5788, BAL9141, imipenem, ertapenem, meropenem, astreonam,clavulanate, sulbactam, tazobactam, streptomycin, neomycin, kanamycin,paromycin, gentamicin, tobramycin, amikacin, netilmicin, spectinomycin,sisomicin, dibekalin, isepamicin, tetracycline, chlortetracycline,demeclocycline, minocycline, oxytetracycline, methacycline, doxycycline,erythromycin, azithromycin, clarithromycin, telithromycin, ABT-773,lincomycin, clindamycin, vancomycin, oritavancin, dalbavancin,teicoplanin, quinupristin and dalfopristin, sulphanilamide,para-aminobenzoic acid, sulfadiazine, sulfisoxazole, sulfamethoxazole,sulfathalidine, linezolid, nalidixic acid, oxolinic acid, norfloxacin,perfloxacin, enoxacin, ofloxacin, ciprofloxacin, temafloxacin,lomefloxacin, fleroxacin, grepafloxacin, sparfloxacin, trovafloxacin,clinafloxacin, gatifloxacin, moxifloxacin, gemifloxacin, sitafloxacin,metronidazole, daptomycin, garenoxacin, ramoplanin, faropenem,polymyxin, tigecycline, AZD2563, and trimethoprim.

Local Anesthetics

Exemplary local anesthetics which can be used in the methods andcompositions of the invention include, without limitation, cocaine,procaine, lidocaine, prilocaine, mepivicaine, bupivicaine, articaine,tetracaine, chloroprocaine, etidocaine, and ropavacaine.

Antispasmodic

Exemplary antispasmodics which can be used in the methods andcompositions of the invention include, without limitation, atropine,belladonna, bentyl, cystospaz, detrol (tolterodine), dicyclomine,ditropan, donnatol, donnazyme, fasudil, flexeril, glycopyrrolate,homatropine, hyoscyamine, levsin, levsinex, librax, malcotran, novartin,oxyphencyclimine, oxybutynin, pamine, tolterodine, tiquizium, prozapine,and pinaverium.

The following examples are put forth so as to provide those of ordinaryskill in the art with a complete disclosure and description of how themethods and compounds claimed herein are performed, made, and evaluated,and are intended to be purely exemplary of the invention and are notintended to limit the scope of what the inventors regard as theirinvention.

The following acronyms denote the listed compounds used in thepreparation of the polymers, polymer complexes, and polymer conjugatesdescribed herein.

-   AEMA aminoethyl methacrylate-   ALLYL allyl alcohol-   ASA acetylsalicylic acid-   BAL poly(difluoromethylene),α-fluoro-ω-(2-hydroxyethyl)-   BHT butylated hydroxy toluene-   BPO benzoyl peroxide-   C8 1-octanol-   CDCl₃ deuterated chloroform-   DBDL dibutyltin dilaurate-   DCM dichloromethane-   DMAc dimethylacetamide-   DMAP 4-(dimethyamino)pyridine-   DMF dimethylformamide-   DMSO dimethylsulphoxide-   EDC 1-ethyl-3-(3-dimethylamino-propyl)carbodiimide.HCl-   EVA poly(ethylene-co-vinyl acetate)-   FEO1 4,4,5,5,6,6,7,7,8,8,9,9,10,10,11,11    heptadecafluoro-2-hydroxyundecyl acrylate-   FEO2 1H, 1H, 2H, 3H nonafluorohept-2-en-ol-   FEO3 3-(perfluoro-3-methylbutyl)-2-hydroxypropyl methacrylate-   HEMA hydroxyethyl methacrylate-   HCl hydrochloric acid-   HMP 2-hydroxy-2-methylpropiophenone-   KBr potassium bromide-   LDI lysine diisocyanate-   MAA methacrylic acid-   MeOH methanol-   MgSO₄ magnesium sulphate-   MMA methyl methacrylate-   NaOH sodium hydroxide-   PBS phosphate buffer solution-   PCL polycaprolactone-   PSi polydimethylsiloxane-bis(3-aminopropyl) terminated-   PTMO polytetramethylene oxide-   PTX paclitaxel-   SIBS poly(stryrene-isobutylene-styrene)-   TEA triethylamine-   TEGMA triethylene glycol dimethacrylate-   TFAc trifluoroacetic acid-   THF tetrahydrofuran-   VP 1-vinyl-2-pyrrolidone-   List of monomers: methacrylic acid, isobutyl acrylate, tertiarybutyl    acrylate, tertiarybutyl methacrylate, 2-hydroxyethyl acrylate,    2-hydroxypropyl acrylate, butanediol monoacrylate, ethyldiglycol    acrylate, lauryl acrylate, dimethylaminoethyl acrylate,    dihydrodicyclopentadienyl acrylate, N-vinylformamid, cyclohexyl    methacrylate, 2-isocyanotomethacrylate, glycidyl methacrylate,    cyanoacrylate, isobornyl acrylate, 4-hydroxybutyl vinyl ether,    di((meth)ethylene glycol)vinyl ether, maleic and fumaric acid,    triethylene glycol dimethacrylate, 1,6 hexanediol methacrylate, 1,4    butanediol dimethacrylate, and urethane dimethacrylate.-   List of initiators: 1,1′-Azobis(cyclohexanecarbonitrile),    2,2′-Azobisisobutyronitrile (AIBN),    2,2′-Azobis[2-(2-imidazolin-2-yl)propane]dihydrochloride, Tert-Butyl    peracetate, 4,4-Azobis(4-cyanovaleric acid),    2,2′-Azobis[2-(2-imidazolin-2-yl)propane]dihydrochloride,    2,2′-Azobis[2-(2-imidazolin-2-yepropane]disulfate dihydrate,    2,2′-Azobis(2-methylpropionamidine)dihydrochloride,    2,2′-Azobis[N-(2-carboxyethyl)-2-methylpropionamidine]hydrate,    2,2′-Azobis{2-[1-(2-hydroxyethyl)-2-imidazolin-2-yl]propane}dihydrochloride,    2 Peracetic acid, 2′-Azobis[2-(2-imidazolin-2-yl)propane],    2,2′-Azobis(1-imino-1-pyrrolidino-2-ethylpropane)dihydrochloride,    2,2′-Azobis{2-methyl-N-[1,1-bis(hydroxymethyl)-2-hydroxyethl]propionamide},    2,2′-Azobis[2-methyl-N-(2-hydroxyethyl)propionamide],    2,2′-Azobis(4-methoxy-2,4-dimethyl valeronitrile),    2,2′-Azobis(2,4-dimethyl valeronitrile), Dimethyl    2,2′-azobis(2-methylpropionate), 2,2′-Azobis(2-methylbutyronitrile),    1,1′-Azobis(cyclohexane-1-carbonitrile),    2,2′-Azobis[N-(2-propenyl)-2-methylpropionamide],    1-[(1-cyano-1-methylethyl)azo]formamide,    2,2′-Azobis(N-butyl-2-methylpropionamide),    2,2′-Azobis(N-cyclohexyl-2-methylpropionamide), Tert-Amyl    peroxybenzoate, Benzoyl peroxide, Potassium persulphate,    2,2-Bis(tert-butylperoxy)butane,    1,1-Bis(tert-butylperoxy)cyclohexane,    2,5-Bis(tert-butylperoxy)-2,5-dimethyl-3-hexyne,    Bis(1-(tert-butylperoxy)-1-methylethyl)benzene, 1,1-B    is(tert-butylperox)-3,3,5-trimethylcyclohexane, Tert-butyl    hydroperoxide, Tert-butyl peroxide, Cyclohexanone peroxide,    2,4-pentadione peroxide, Lauroyl peroxide, Dicumyl peroxide,    Tert-butyl peroxybenzoate, Cumene hydroperoxide, Tert-butylperoxy    isopropyl carbonate, Camphorquinone,    Diphenyl(2,4,6-trimethylbenzoyl)phosphine oxide,    2-tert-Butylanthraquinone, 9,10-Phenanthrenequinone,    Anthraquinone-2-sulfonic acid sodium salt monohydrate,    Phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide,    1-Hydroxycyclohexyl phenyl ketone, 2-Hydroxy-2-methylpropiophenone,    2-Benzyl-2-(dimethylamino)-4′-morpholinobutyrophenone,    2,2-Diethoxyacetophenone,    2-Hydroxy-4′-(2-hydroxyethoxy)-2-methylpropiophenone,    2-Methyl-4′-(methylthio)-2-morpholinopropiophenone,    3′-Hydroxyacetophenone, 4′-Ethoxyacetophenone,    4′-Hydroxyacetophenone, 4′-Phenoxyacetophenone,    4′-tert-Butyl-2′,6′-dimethylacetophenone,    Diphenyl(2,4,6-trimethylbenzoyl)phosphine    oxide/2-hydroxy-2-methylpropiophenone,    2,2-Dimethoxy-2-phenylacetophenone, 4,4′-Dimethoxybenzoin,    3-Methylbenzophenone, Benzoin, 3-Hydroxybenzophenone,    3,4-Dimethylbenzophenone, 2-Methylbenzophenone,    Benzophenone-3,3′,4,4′-tetracarboxylic dianhydride,    4-Methylbenzophenone, 4-Hydroxybenzophenone, 4-Benzoylbiphenyl,    4-(Dimethylamino)benzophenone, 4-(Diethylamino)benzophenone,    Michler's ketone, 4,4′-Bis[2-(1-propenyl)phenoxy]benzophenone,    mixture of cis and trans 4,4′-Dihydroxybenzophenone,    4,4′-Bis(diethylamino)benzophenone, Methyl benzoylformate, Benzoin    methyl ether, Benzoin isobutyl ether, 4,4′-Dimethylbenzil, Benzoin    ethyl ether, (4-Bromophenyl)diphenylsulfonium triflate,    (4-Chlorophenyl)diphenylsulfonium triflate, Triphenylsulfonium    perfluoro-1-butanesufonate, N-Hydroxy-5-norbornene-2,3-dicarboximide    perfluoro-1-butanesulfonate, Triphenylsulfonium triflate,    Diphenyliodonium 9,10-dimethoxyanthracene-2-sulfonate,    Tris(4-tert-butylphenyl)sulfonium perfluoro-1-butanesulfonate, and    Tris(4-tert-butylphenyl)sulfonium triflate.

Experimental Protocols

Purification and analytical methods mentioned in the examples aredescribed below.

Cationic Solid Phase Extraction (SCX-SPE): A pre-packed cationic silicagel column (plastic) is used to remove small cationic compounds from thereaction mixtures.

Fluorous Solid Phase Extraction (F-SPE): SPE substrates modified withperfluorinated ligands (F-SPE) are used to selectively retainperfluorinated oligomers, allowing the separation of non-fluorinatedcompounds.

Contact angle analysis: Droplets of MilliQ water are applied to films,and the shape of the droplets are analyzed using a Kruss DSA instrument.

Elemental analysis: samples are combusted, and the liberated fluorine isabsorbed into water and analyzed by ion-selective electrode.

FTIR analysis: a sample is dissolved as a 20 mg/mL solution in asuitable volatile solvent and 50 μL of this solution is cast on a KBrdisk. Once dried, the sample is analyzed.

Gel extraction: samples of film are weighed and then extracted with asuitable solvent for 12 hours. The films are removed from the solvent,weighed, and then vacuum dried and weighed again. Gel content iscalculated as the percentage of mass that is not extracted. Swell ratiois calculated at the percentage increase in mass before the sample isvacuum dried.

GPC analysis: samples are dissolved as a 20 mg/mL solution in a suitablesolvent (THF, dioxane, DMF) and are analyzed using a polystyrene columncalibrated with polystyrene standards.

NMR: samples are dissolved at 20 mg/mL in a suitable solvent and areanalyzed using a 300 or 400 MHz NMR spectrometer.

SEM: surfaces were coated with gold.

Tensile testing: films are cut into test specimens and are analyzedaccording to ASTM D 1708 guidelines.

XPS analysis: films are analyzed using a 90° take-off angle.

EXAMPLE 1 Synthesis of α,ω-BAL-Poly(LDI(HEMA)/PTMO) with Pendent VinylGroups (Compound 2)

Polytetramethylene oxide (PTMO) (15 grams, 14 mmol) was weighed into a500 mL 2-neck flask and degassed overnight at 30° C., and was thendissolved in anhydrous DMAc (40 mL) under N₂. LDI (5.894 g, 28 mmol) wasweighed into a 2-neck flask and was dissolved in anhydrous DMAc (40 mL)under N₂. DBDL was added to the LDI solution, and this mixture was addeddropwise to the PTMO solution. The flask was kept sealed and maintainedunder N₂ at 70° C. for two hours. Fluoroalcohol (13.151 g, 31 mmol) wasweighed into a 2-neck flask and degassed at room temperature, wasdissolved in anhydrous DMAc (40 mL) and was added dropwise to thereaction mixture. The reaction solution was sealed under N₂ and wasstirred overnight at room temperature. The product was precipitated inwater (3 L), washed several times, and dried. The product was dissolvedin MeOH and the tin catalyst was extracted by SCX SPE. The final product(Compound 1-ester) was dried under vacuum. ¹H NMR (300 MHz, CDCl₃) δ(ppm) 4.24-4.46 (—CH₂—O, BAL), 3.94-4.13 (—CH₂—O—CO PTMO), 3.74 (CH₃,LDI), 3.28-3.50 (CH₂—O PTMO), 2.98-3.28 (CH ₂—NH, LDI), 2.29-2.60(—CH₂—CF₂—, BAL), 1.16-1.96 (PTMO and LDI CH₂). ¹⁹F NMR (300 MHz, CDCl₃)δ (ppm) −81.23 (CF₃), −114.02 (CF₂), −122.34 (CF₂), −123.34 (CF₂),−123.30 (CF₂), −124.03 (CF₂), −126.56 (CF₂). Elemental analysis:theoretical based on reagent stoichiometry (%): C, 48.49; H, 6.57; F,23.85; N, 2.81; O, 18.27. Measured: C, 48.70; H, 6.56; F, 22.81; N,2.63. HPLC analysis (reversed phase, C18 column, methanol and pH 9 PBSmobile phase (gradient)): retention time of 39.5 minutes. DSC analysis:Tg=−66.6° C. IR analysis was in accordance with the chemical structure:3327.29 cm⁻¹ v(N—H) H-bonded, 2945.10 cm⁻¹ v(C—H) CH₂ asymmetricstretching, 2865.69 cm⁻¹ v(C—H) CH₂ symmetric stretching, 1717.91 cm⁻¹v(C═O) urethane amide, 1533.54 cm⁻¹ v(C—N) stretching mode, 1445.56 cm⁻¹v(C—N) stretching mode, 1349.31 cm⁻¹ v(C—O) stretching, 1400-1000 cm⁻¹v(C—F) monofluoroalkanes absorb to the right in the range, whilepolyfluoroalkanes give multiple strong bands over the range from1350-1100 cm⁻¹.

Compound 1-ester (15.0 g, ˜16 mmol ester) was weighed into a flask,dissolved in MeOH (150 mL) and once dissolved, 1N NaOH solution (17 mL)was added dropwise. After six hours of stirring at room temperature, thesolution was neutralized using 1N HCl (17.7 mL), and the product wasprecipitated in water, washed with water, and dried under vacuum at 60°C. The conversion of ester groups to acid functional groups wasconfirmed by NMR analysis. Proton NMR indicated the disappearance ofmethoxy groups at 3.75 ppm. ¹⁹F NMR (300 MHz, CDCl₃) δ (ppm) −81.23(CF₃), −114.02 (CF₂), −122.34 (CF₂), −123.34 (CF₂), −123.30 (CF₂),−124.03 (CF₂), −126.56 (CF₂). HPLC analysis: retention time of 33.4minutes (Compound 1-acid). Reversed phase HPLC, C18 column, MeOH and pH9 PBS mobile phase (gradient). DSC analysis: Tg=−65° C. Elementalanalysis: theoretical based on reagent stoichiometry (%): C, 47.96; H,6.48; F, 24.19; N, 2.86; O, 18.53. Measured: C, 46.92; H, 6.16; F,26.43; N, 2.94. Compound 1-acid (10.0 gram, ˜8 mmol acid), DMAP (0.488gram, 4 mmol), HEMA (6.247 gram, 48 mmol) and DCM (50 mL) were added toa 250 mL flask, and stirred until all compounds were dissolved. EDC(4.600 gram, 24 mmol) was added to the DCM solution, and once the EDCwas dissolved, the solution was stirred at room temperature for 24 hoursunder N₂ and protection from light. The reaction mixture was reduced toa viscous liquid by rotary evaporation (25° C.) and washed three timeswith water (3×400 mL). The washed product was dissolved in diethyl ether(100 mL, 100 ppm BHT), and water was removed by mixing the solution withMgSO₄ for 1 hour. The solution was clarified by gravity filtration intoa 250 mL flask, and the solvent was removed by rotary evaporation (25°C.). The product (Compound 2) was re-dissolved in DMF and was purifiedby fluorous SPE (F-SPE) and recovered by rotary evaporation. ¹H NMR (300MHz, CDCl₃) δ (ppm) 6.09-6.15 (HEMA vinyl H), 5.58-5.63 (HEMA vinyl H),4.27-4.49 (—CH₂—O, BAL, CH₂HEMA), 4.01-4.15 (—CH₂—O—CO PTMO), 3.75(small CH₃ signal, LDI), 3.31-3.50 (CH₂—O PTMO), 3.07-3.23 (CH ₂—NH,LDI), 2.36-2.56 (—CH₂—CF₂—, BAL), 1.91-1.96 (HEMA CH₃) 1.27-1.74 (PTMOand LDI CH₂). ¹⁹F NMR (300 MHz, CDCl₃) δ (ppm) −81.23 (CF₃), −114.02(CF₂), −122.34 (CF₂), −123.34 (CF₂), −123.30 (CF₂), −124.03 (CF₂),−126.56 (CF₂). GPC analysis: the product was dissolved in dioxane andrun on a GPC system with a polystyrene column and UV detector. No freeHEMA monomer detected in this analysis. HPLC analysis: retention time of39.8 minutes (Compound 2), no free HEMA monomer detected in thisanalysis. Reversed phase HPLC, C18 column, MeOH and pH 9 PBS mobilephase (gradient). IR analysis was in accordance with the chemicalstructure: 3318 cm⁻¹ v(N—H) H-bonded, 2935 cm⁻¹ v(C—H) CH₂ asymmetricstretching, 2854 cm⁻¹ v(C—H) CH₂ symmetric stretching, 1722 cm⁻¹ v(C═O)urethane amide, 1634 cm⁻¹ (vinyl C═C stretching), 1532 cm⁻¹ v(C—N)stretching mode, 1456 cm⁻¹ v(C—N) stretching mode, 1349.31 cm⁻¹ v(C—O)stretching, 1400-1000 cm⁻¹ v(C—F) monofluoroalkanes absorb to the rightin the range, while polyfluoroalkanes give multiple strong bands overthe range from 1350-1100 cm⁻¹. Elemental analysis: theoretical based onreagent stoichiometry (%): C, 49.64; H, 6.53; F, 21.71; N, 2.56; O,19.55. Measured: C, 50.78; H, 6.89; F, 19.33; N, 2.50.

EXAMPLE 2 Synthesis of α,ω-BAL-Poly(LDI(Allyl)/PTMO) with Pendent VinylGroups (Compound 3)

Compound 1-acid (12.03 g, 12.11 mmol), DMAP (0.74 g, 6.05 mmol), allylalcohol (4.22 g, 72.64 mmol) and anhydrous DCM (100 mL) were weighedinto a 250 mL flask equipped with a stir bar. The contents of the flaskwere magnetically stirred until all ingredients were dissolved. Then EDC(6.96 g, 36.32 mmol) white solid was added to the flask. The reactionflask was wrapped with aluminium foil and the solution was stirred atroom temperature under N₂ for 3 days. After 3 days, DCM was removed byrotary evaporator at 25° C. to yield a viscous crude product. The crudeproduct was washed three times with aqueous HCl (each time using amixture of 30 mL of 0.1N HCl and 60 mL distilled water), and finallywith distilled water (100 mL) itself. Extracting organic solublematerials (includes the desired product) into diethyl ether solvent,drying the organic solvent over solid MgSO₄, and removing the solvent byrotary evaporator at room temperature yielded a slightly yellow liquid.Column chromatography of the liquid using first diethyl ether, diethylether/DCM (50/50, w/w) mixture, DCM itself, and then a DCM/MeOH (80/20,w/w) mixture yielded an opaque liquid (Compound 3), 6.34 g (50.6%).Elemental analysis: Theoretical based on reagent stoichiometry (%): C,49.61; H, 6.60; F, 23.24; N, 2.75; O, 17.80. Measured: C, 49.47; H,6.64; F, 24.87; N, 2.65. ¹H-NMR (CDCl₃, 300 MHz): δ 5.92 (CH₂CHCH₂,allyl), 5.30 (CH₂CHCH ₂ (geminal, allyl)), 4.74 (NH), 4.64 (CH ₂CHCH₂,allyl), 4.37 (OCH₂, BAL, and NHCH, LDI), 4.08 (NH(O)COCH ₂, PTMO), 3.42(OCH ₂CH₂, PTMO), 3.15 (NHCH ₂, LDI), 2.46 (OCH₂CH ₂, BAL), 1.87-1.20(CH₂, LDI, and CH₂, PTMO). Based on integration of BAL at 2.47 ppm andallyl alcohol at 6.12 ppm, the amount of allyl alcohol attached onto theoligomer after the reaction was estimated to be 72%. The absolutenumber-average molecular weight (Mn) was estimated, usingpentafluorobenzene (6.90 ppm) as the external reference against BAL at2.46 ppm, PTMO at 3.42 ppm, LDI at 3.15 ppm and allyl at 5.92 ppm, to be1845 g/mol. ¹⁹F-NMR (CDCl₃, 300 MHz, CFCl₃ as the internal referencestandard): δ −81.26 (CF₃), −114.02 (CF₂), −122.41 (CF₂), −123.40 (CF₂),−124.15 (CF₂), −126.75 (CF₂). GPC analysis: the product was dissolved indioxane and run on a GPC system with a polystyrene column and UVdetector: no free monomer was detected. HPLC analysis: retention time of40 minutes (Compound 3), no free allyl monomer detected. Reversed phaseHPLC, C18 column, MeOH and pH 9 PBS mobile phase (gradient). FT-IR (KBrdisc, neat): 3318 (N—H, broad), 2933-2794 (aliphatic C—H), 1704 (C═O),1650 (C═C), 1530, 1436, 1355, 1255, 1100, 843, 809, 778, 745, 734, 707,697 cm⁻¹.

EXAMPLE 3 Synthesis of α,ω-Allyl-Poly(LDI(BAL)/PTMO) with Pendent VinylGroups (Compound 4)

Compound 4 was prepared by conjugating fluorinated groups to Compound 13from Example 11.

Compound 13-acid from Example 11 (7.52 g, 10.95 mmol), DMAP (0.67 g,5.48 mmoL), BAL (23.06 g, 65.71 mmol, M_(n)=351 Daltons determined by¹H-NMR using pentafluorobenzene as the external reference), andanhydrous DCM (100 g) were weighed into a 250 mL flask equipped with astir bar. The flask was magnetically stirred until all ingredients weredissolved. Then EDC (6.30 g, 32.86 mmol) white solid was added to theflask. The reaction flask was wrapped with aluminium foil and thesolution was stirred at room temperature under N₂ for 5 days. After 5days, DCM was removed by rotary evaporator at 25° C. to yield a yellowcrude product. The crude product was washed three times with aqueous HCl(each time using a mixture of 30 mL of 0.1N HCl and 60 mL distilledwater), and finally with distilled water (100 mL) itself. Extractingorganic soluble materials (includes the desired product) into diethylether solvent, drying the organic solvent over solid MgSO₄, and removingthe solvent by rotary evaporator at room temperature yielded a slightlyyellow liquid. The liquid was dissolved in a small amount of acetone,and dropwise the acetone solution was added into a beaker containingmethoxyperfluorobutane solvent (150 g), forming an emulsion.Centrifuging the emulsion at 3400 rpm and discarding the fluorinatedsolvent yielded a clear liquid, Compound 4. Elemental analysis:Theoretical based on reagent stoichiometry (%): C, 49.61; H, 6.60; F,23.24; N, 2.74; O, 17.80. Measured: C, 53.42; H, 7.76; F, 16.25; N,2.70. ¹H-NMR (CDCl₃, 300 MHz): δ 5.92 (CH₂CHCH₂, allyl), 5.25 (CH₂CHCH ₂(geminal, allyl)), 4.74 (NH), 4.57 (CH ₂CHCH₂, allyl), 4.44 (OCH ₂,BAL), 4.32 (NHCH, LDI), 4.08 (NH(O)COCH ₂, PTMO), 3.42 (OCH ₂, PTMO),3.17 (NHCH ₂, LDI), 2.50 (OCH₂CH ₂, BAL), 1.87-1.20 (CH₂, LDI, and CH₂,PTMO). Based on integration of BAL at 2.47 ppm and LDI at 3.17 ppm, theamount of BAL attached onto the oligomer after the reaction wasestimated to be 67%. The absolute number-average molecular weight (Mn)was estimated, using pentafluorobenzene (6.90 ppm) as the externalreference against allyl at 5.92 ppm, PTMO at 3.42 ppm, BAL at 2.50 ppmand LDI at 3.17 ppm, to be 2007 g/mol. ¹⁹F-NMR (CDCl₃, 300 MHz, CFCl₃ asthe internal reference standard): δ −81.14 (CF₃), −113.86 (CF₂), −122.19(CF₂), −123.30 (CF₂), −123.89 (CF₂), −126.46 (CF₂). GPC analysis: theproduct was dissolved in dioxane and run on a GPC system with apolystyrene column and UV detector: no free monomer was detected. HPLCanalysis: no free monomer detected. Reversed phase HPLC, C18 column,MeOH and pH 9 PBS mobile phase (gradient). FTIR (KBr, neat): 3315 (N—H,broad), 2933-2794 (aliphatic C—H), 1720 (C═O), 1644 (C═C), 1530, 1436,1365, 1247, 1110, 778, 742, 733, 706, 696 cm⁻¹.

EXAMPLE 4 Synthesis of α,ω-BAL-Poly(LDI/PTMO) with Pendent Amino EthylMethacrylate (Compound 5)

Compound 1-acid (0.5 gram, ˜0.43 mmol acid) was weighed into a 2-neckflask, degassed, and dissolved in DMF (5 mL). The solution was chilledto 0° C., and to it was added EDC (0.245 g, 1.28 mmol) pre-dissolved inDMF (1 mL). The solution was raised to room temperature and stirredunder nitrogen atmosphere and protection from light for two hours. Then,DMAP (0.026 g, 0.21 mmol) and AEMA.HCl (0.035 g, 0.21 mmol) were addedto the flask, and stirred till all compounds were dissolved. Thesolution was kept stirring for one hour. The product (Compound 5) wasprecipitated and washed with water. The product was resuspended inacetone, dried with MgSO4, and the solvent was evaporated off at roomtemperature. ¹H NMR (400 MHz, CDCl₃) δ (ppm) 6.13 (AEMA vinyl H), 5.61(AEMA vinyl H), 4.36 (O—CH₂— BAL), 4.25 (CH₂, AEMA), 4.07 (—CH₂—O—COPTMO), 3.75 (minor LDI ester CH₃), 3.41 (CH₂—O PTMO), 3.18 (CH ₂—NH,LDI), 2.45 (—CH₂—CF₂— BAL), 1.95 (—CH₃, AEMA), 1.62 (PTMO and LDI CH₂).GPC analysis: Compound 5 was dissolved in THF and run on a GPC systemwith a polystyrene column and UV detector. No free AEMA monomer detectedin this analysis.

EXAMPLE 5 Synthesis of α,ω-FEO1-Poly(LDI/PTMO) with Pendent Vinyl Groups(Compound 6)

PTMO (10 g, 10 mmol, degassed) was dissolved in anhydrous DMAc (50 mL).LDI (4.11 g, 20 mmol, distilled) and DBDL catalyst were dissolved inanhydrous DMAc (25 mL) and added dropwise to the PTMO solution, and thereaction was maintained at 70° C. for two hours under N₂. Thehydroxyperfluoroacrylate(4,4,5,5,6,6,7,7,8,8,9,9,10,10,11,11heptadecafluoro-2-hydroxyundecyl acrylate) (FEO1, 12.058 g, 22 mmol) wasdissolved in DMAc (25 mL) with DBDL and added dropwise to the reactionsolution. The reactor was kept sealed under N₂ and stirred overnight atroom temperature. The product was precipitated in water (2 L) andre-dissolved in diethyl ether (100 mL, 100 ppm BHT), dried with MgSO₄and filtered. The ether solution was dropped into hexane (400 mL) toprecipitate the product and extract un-reacted reagent. The hexane wasdecanted and the solvent extraction procedure was repeated twice. Thepurified product (Compound 6) was dissolved in diethyl ether (50 mL),and the solvent removed by rotary evaporation at room temperature. ¹HNMR (400 MHz, CDCl₃) δ (ppm) 6.40-6.52 (FEO1 vinyl H), 6.09-6.23 (FEO1vinyl H), 5.80-5.95 (FEO1 vinyl H), 4.15-4.53 (C—H FEO1, O—CH₂— FEO1),4.00-4.15 (—CH₂—O—CO PTMO), 3.75 (LDI ester CH₃), 3.31-3.50 (CH₂—OPTMO), 3.05-3.25 (CH ₂—NH, LDI), 2.35-2.61 (—CH₂—CF₂— FEO1), 1.25-1.73(PTMO and LDI CH₂). GPC analysis: Compound 6 was dissolved in dioxaneand run on a GPC system with a polystyrene column and UV detector. Nofree FEO1 monomer detected in this analysis. IR analysis: 1634 cm⁻¹(C═C)

EXAMPLE 6 Synthesis of α,ω-FEO2-Poly(LDUPTMO) with Pendent Vinyl Groups(Compound 7)

PTMO (2.012 g, 2 mmol, degassed) was dissolved in anhydrous DMAc (10mL). LDI (0.848 g, 4 mmol, distilled) and DBDL catalyst were dissolvedin anhydrous DMAc (5 mL) and was added dropwise to the PTMO solution.The pre-polymer reaction was maintained at 60-70° C. for two hours underN₂. The perfluor-en-ol (1H, 1H, 2H, 3H nonafluorohept-2-en-ol) (FEO2,1.214 g, 4.4 mmol) was dissolved in DMAc (5 mL) with DBDL and addeddropwise to the pre-polymer solution. The reactor was kept sealed underN₂ and stirred overnight at room temperature. The product wasprecipitated in water (0.5 L) and re-dissolved in diethyl ether (20 mL,100 ppm BHT), dried with MgSO₄ and filtered. The ether solution wasdropped into hexane (80 mL) to precipitate the product and extractun-reacted reagent. The hexane was decanted and the solvent extractionprocedure was repeated twice. The purified product (Compound 7) wasdissolved in diethyl ether (50 mL), and the solvent removed by rotaryevaporation at room temperature. ¹H NMR (400 MHz, CDCl₃) δ (ppm)6.37-6.51 (vinyl H, FEO2), 5.76-5.95 (vinyl H, FEO2), 5.80-5.95 (FEO1vinyl H), 4.66-4.87 (CH₂, FEO2), 4.24-4.38 ((—CH₂—O—CO LDI), 3.97-4.12(—CH₂—O—CO PTMO), 3.66-3.77 (LDI ester CH₃), 3.27-3.52 (CH₂—O PTMO),3.05-3.23 (CH—NH, LDI), 1.28-1.94 (PTMO and LDI CH₂). GPC analysis:(Compound 7) was dissolved in dioxane and run on a GPC system with apolystyrene column and UV detector. No free FEO2 monomer detected inthis analysis. IR analysis: 1634 cm⁻¹ (C═C).

EXAMPLE 7 Synthesis of α,ω-FEO3-Poly(LDI/PTMO) with Pendent Vinyl Groups(Compound 8)

PTMO (10 g, 10 mmol, degassed) was dissolved in anhydrous DMAc (50 mL).LDI (4.241 g, 20 mmol, distilled) and DBDL catalyst were dissolved inanhydrous DMAc (22 mL) and was added dropwise to the PTMO solution. Thepre-polymer reaction was maintained at 60-70° C. for two hours under N₂.The hydroxyperfluoroacrylate(3-(perfluoro-3-methylbutyl)-2-hydroxypropyl methacrylate) (FEO3, 9.068g, 22 mmol) was dissolved in DMAc (23 mL) with DBDL and added dropwiseto the pre-polymer solution. The reactor was kept sealed under N₂ andstirred overnight at room temperature. The product was precipitated inwater (2 L) and re-dissolved in diethyl ether (100 mL, 100 ppm BHT),dried with MgSO₄ and filtered. The ether solution was dropped intohexane (400 mL) to precipitate the product and extract un-reactedreagent. The hexane was decanted and the solvent extraction procedurewas repeated two times. The purified product (Compound 8) was dissolvedin diethyl ether (50 mL), and the solvent removed by evaporation in aflow hood at room temperature. ¹H NMR (400 MHz, CDCl₃) δ (ppm) 6.10-6.16(FEO3 vinyl H), 5.66-5.89 (FEO3 vinyl H), 4.27-4.41 (—O—CH₂— FEO3),4.15-4.27 (—O—CH₂— FEO3) 4.00-4.14 (—CH₂—O—CO PTMO), 3.75 (LDI esterCH₃), 3.27-3.52 (CH₂—O PTMO), 3.05-3.21 (CH ₂—NH, LDI), 2.34-2.61(—CH₂—CF₂— FEO3), 1.90-1.99 (CH₃, FEO3), 1.22-1.90 (PTMO and LDI CH₂).GPC analysis: Compound 8 was dissolved in dioxane and run on a GPCsystem with a polystyrene column and UV detector. No free FEO3 monomerdetected in this analysis. IR analysis: 1634 cm⁻¹ (C═C).

EXAMPLE 7′ Synthesis of α,ω-C8-Poly(LDI(hydroxyperfluoroacrylate)/PTMO)with Pendent Vinyl Groups (Compound 9′)

PTMO (10.0 g, 10.0 mmol) was weighed into a 250 mL round bottom flaskequipped with a stir bar. The flask was heated to 30° C. using an oilbath, and was held under vacuum for 2 hours to remove trace amounts ofwater. The flask was cooled to room temperature and anhydrous DMAc (50mL) was added to dissolve the PTMO. LDI (3.18 g, 15.0 mmol), DBDL andanhydrous DMAc (5 mL) were mixed and transferred to the flask viasyringe. The reaction flask was heated to 70° C. in an oil bath, and thereaction mixture was stirred for 2 hours. Then, 1-octanol (1.43 g, 11mmol) was introduced into the reactor by syringe injection, and thereaction mixture was kept stirring at room temperature overnight (17hours). The next day, the reaction mixture was precipitated into 3 L ofdistilled water. The wash procedure was repeated twice with distilledwater (3 L). The product was dried under a vacuum to yield the finalproduct, Compound 8′-ester. ¹H-NMR (CDCl₃, 300 MHz): δ 4.07 (NH(O)COCH₂, PTMO), 3.74 (—OCH ₃, LDI), 3.41 (OCH ₂CH₂CH₂CH ₂O, PTMO, and (O)COCH₂(CH₂)₆CH₃, octanol), 3.16 (NHCH ₂, LDI), 1.62 (CHCH ₂CH ₂CH ₂CH₂NH,LDI, OCH₂CH ₂CH ₂CH₂O, PTMO, and (O)COCH₂(CH ₂)₆CH₃, octanol), 0.88((O)COCH₂(CH₂)₆CH ₃, octanol). The MW of Compound 8′-ester was highercompared to Compound 1 MW, as detected by GPC measurement.

Compound 8′-ester (5.0 g, 5.2 mmol ester) was weighed in a 250 mL beakerand was dissolved in acetone (50 mL). NaOH 1.0N (5.18 mL) was addeddropwise to the beaker and the mixture was stirred at room temperaturefor 6 hours. The reaction mixture was then neutralized with 5.70 mL of1.0 N aqueous HCl, and additional water was added to yield a whiteprecipitate. Once the wash water was removed, the intermediate productwas recovered and was washed twice with distilled water (1.0 L). Thefinal product was dried under vacuum for 18 hours to yield an opaqueviscous product, Compound 8′-acid. ¹H-NMR (CDCl₃, 300 MHz): the singletat 3.74 (—OCH₃) was used to monitor the degree of hydrolysis of theester group.

Compound 8′-acid (0.43 g, 0.46 mmol acid), DMAP (27.2 mg, 0.22 mmoL),FEO1 (1.46 g, 2.67 mmol) and anhydrous DCM (7 mL) were weighed into a 50mL flask equipped with a stir bar. The contents of the flask weremagnetically stirred until all ingredients were dissolved. Then EDC(0.256 g, 1.3 mmol) white solid was added to the flask. The reactionflask was wrapped with aluminium foil and the solution was stirred atroom temperature under N₂ overnight. The following day, the DCM wasremoved by rotary evaporation at 25° C. to yield a crude product. Thecrude product was washed using solvent and water extraction, dried overMgSO₄, and the solvent was removed by rotary evaporation. The finalproduct (Compound 9′) was dried under vacuum. ¹H-NMR (CDCl₃, 300 MHz): δ6.45, 6.19, 5.43 (vinyl H, FEO1), 4.07 (NH(O)COCH ₂, PTMO), 3.74 (minor—OCH ₃, LDI), 3.41 (OCH ₂CH₂CH₂CH ₂O, PTMO, and (O)COCH ₂(CH₂)₆CH₃,octanol), 3.16 (NHCH ₂, LDI), 2.42 (—CH₂—CF₂—, FEO1), 1.62 (CHCH ₂CH ₂CH₂CH₂NH, LDI, OCH₂CH ₂CH ₂CH₂O, PTMO, and (O)COCH₂(CH ₂)₆CH₃, octanol),0.88 ((O)COCH₂(CH₂)₆CH ₃, octanol). GPC analysis: Compound 9′ wasdissolved in dioxane and run on a GPC system with a polystyrene columnand UV detector. No free FEO1 monomer was detected in this analysis.

The above conjugation of FEO1 was reproduced using FEO3. Compound8′-acid (2.5 g, 2.59 mmol acid), DMAP (0.158 g, 1.29 mmoL), FEO3 (6.396g, 15.52 mmol) and anhydrous DCM (13 mL) were weighed into a 100 mLflask equipped with a stir bar. The contents of the flask weremagnetically stirred until all ingredients were dissolved. Then EDC(1.487 g, 7.76 mmol) was added to the flask. The remaining synthesis andpurification steps were identical to the FEO1 reaction. ¹H-NMR (CDCl₃,300 MHz): δ 6.14, 5.64 (vinyl H, FEO3), 4.07 (NH(O)COCH ₂, PTMO), 3.74(minor —OCH ₃, LDI), 3.41 (OCH ₂CH₂CH₂CH ₂O, PTMO, and (O)COCH₂(CH₂)₆CH₃, octanol), 3.16 (NHCH ₂, LDI), 2.4 (—CH₂—CF₂—, FEO3), 1.94(CH₃, FEO3), 1.62 (CHCH ₂CH ₂CH ₂CH₂NH, LDI, OCH₂CH ₂CH ₂CH₂O, PTMO, and(O)COCH₂(CH ₂)₆CH₃, octanol), 0.88 ((O)COCH₂(CH₂)₆CH ₃, octanol). GPCanalysis: Compound 9′ (b) was dissolved in dioxane and run on a GPCsystem with a polystyrene column and UV detector. No free FEO3 monomerwas detected in this analysis.

EXAMPLE 8 Synthesis of α,ω-BAL-Poly(LDI(HEMA)/PSi) with Pendent VinylGroups (Compound 10)

Poly(dimethylsiloxane), bis(3-aminopropyl) terminated (30.2 g, 12.1mmol, M_(n)=2500, Aldrich) were weighed into a 250 mL round bottom flaskequipped with a stir bar. The flask was heated to 45° C. using an oilbath, and under vacuum pumping for 2 hours to remove trace amounts ofwater. The flask was removed from the oil bath and allowed to cool toroom temperature before it was transferred to a glove box with LDI, BAL,a 1 L bottle containing anhydrous DCM solvent and a flame-dry empty 250mL round bottom flask equipped with a stir bar. In the glove box, LDI(5.13 g, 24.2 mmol) and anhydrous DCM (100 mL) was transferred to theempty flask. Anhydrous DCM (50 mL) was also transferred to the flaskcontaining dry poly(dimethylsiloxane), and the flask was swirled untilthe content completely dissolved. The solution of poly(dimethylsiloxane)was then added dropwise to the flask containing LDI solution as thereaction mixture was stirred at room temperature. The addition completein 10 minutes, and the reaction mixture was kept stirring for another 20minutes. Then, BAL (8.48 g, 24.2 mmol, M_(n)=351 g/mol determined by¹H-NMR using pentafluorobenzene as the external reference) wastransferred into the reactor. The reactor was capped by a rubber septumand removed from the glove box. While the reaction mixture was heated to65° C. in an oil bath under N₂, DBDL (0.02 mL) was transferred to thereactor via. a syringe. The reactor was kept stirring at 65° C.overnight (17 hours). The next day, the reaction mixture was cooled toroom temperature, and DCM solvent was removed by rotary evaporator toyield a liquid product (Compound 9-ester).

Compound 9-ester (30.5 g, 16.8 mmol) and DCM (100 mL) were transferredto a 500 mL flask containing a stir bar. Deionized water (3.33 g, 18.5mmol) and NaOH in MeOH (0.10 N, 185 mL, 18.5 mmol) were added to thereactor. Note that if the ester-precursor solution turned cloudy duringthe addition of NaOH solution and water, more DCM solvent was requireduntil the mixture became transparent. The reaction mixture was keptstirring at room temperature for 8 hours, and then neutralized with a1.0 N HCl_((aq)) (20 mL, 20.0 mmol). Transferred the reaction mixture toa separatory funnel, washed it twice with deionized water and removedorganic solvents by rotary evaporator yielded slightly yellow viscousliquid. Complete removal of residual organic solvents affordedtransparent viscous liquid, Compound 9-acid.

Compound 9-acid (20.8 g, 11.56 mmol), DMAP (0.71 g, 5.78 mmol), HEMA(9.03 g, 69.37 mmol) and anhydrous DCM (150 mL) were transferred into a500 mL flask equipped with a stir bar. The content of the flask weremagnetically stirred until all ingredients were dissolved. Then whitesolid EDC (6.65 g, 34.69 mmol) was added to the flask. The reactionflask was wrapped with aluminium foil and kept stirring at roomtemperature under N₂ for 3 days. After 3 days, DCM was removed by rotaryevaporator at 25° C. to yield a viscous crude product. The crude productwas washed three times with distilled water (150 mL each time).Extracting organic soluble materials into diethyl ether solvent, dryingthe organic solvent over solid MgSO₄, and removing the solvent by rotaryevaporator at room temperature yielded a viscous liquid. The viscousliquid was washed three times with MeOH (HPLC grade, 150 mL each time)to remove unreacted HEMA. MeOH solvent was discarded and removedcompletely by a vacuum pump to afford a transparent viscous liquid,Compound 10.

EXAMPLE 9 Synthesis of α,ω-BAL-Poly(LDI(HEMA)/PCL) with Pendent VinylGroups (Compound 11′)

Polycaprolactone diol (PCL diol) (10 grams, 8 mmol, degassed) wasdissolved in anhydrous DMAc (50 mL). LDI (3.39 g, 16 mmol, distilled)and DBDL catalyst was dissolved in anhydrous DMAc (18 mL) and was addeddropwise to the PCL diol solution. The pre-polymer reaction wasmaintained at 60-70° C. for two hours under N₂. BAL (7.39 g, 18 mmol)and DBDL were dissolved in anhydrous DMAc (25 mL) and were addeddropwise to the pre-polymer solution. The reactor was kept sealed underN₂ and stirred overnight at room temperature. The product (Compound11-ester) was precipitated in water (3 L), re-suspended in acetone, andpurified by passing the acetone solution through SCX SPE columns. Theacetone solution was evaporated at 40° C. in a flow oven, and theproduct was dried under vacuum. PCL diol and Compound 11-ester weredissolved in dioxane and were analyzed by GPC using polystyrene columnsand UV detection: the Compound 11-ester chromatogram does not containun-reacted PCL diol. ¹H NMR (400 MHz, CDCl₃) δ (ppm) 4.28-4.46 (—CH₂—O—CONH—, BAL), 4.16-4.27 (—CH—O—CONH—, PCL), 3.98-4.11 (—CH₂—O—, PCL),3.71-3.77 (CH₃, LDI), 3.09-3.22 (CH ₂—O—CONH—, LDI), 2.38-2.54 (CH₂—CF₂,BAL), 2.26-2.38 (O—CO—CH₂—, PCL), 1.45-1.76 (—CH₂—, PCL), 1.20-1.45(—CH₂—, PCL).

Compound 11-ester (0.5 g, 0.4 mmol LDI ester) was dissolved in acetone(5 mL) and once dissolved, 1 N NaOH (0.4 mL, 0.4 mmol) was added withgood stirring at room temperature for three hours. The product wasneutralized with 1 N HCl (0.4 mL, 0.4 mmol) and water was added tocomplete the precipitation and wash the product. The product (Compound11-acid) was dried under vacuum at 60° C. The conversion of esterfunctional groups to acid groups was monitored by proton NMR analysis.

Compound 11-acid (2.0 gram, ˜2.4 mmol acid), DMAP (0.145 g, 1.19 mmol),HEMA (1.863 g, 14.3 mmol) and DCM (10 mL) were added to a 100 mL flask,and were stirred until all compounds are dissolved. EDC (1.372 g, 7.16mmol) was added to the DCM solution, and once the EDC was dissolved, thesolution was stirred at room temperature for 24 hours under nitrogenatmosphere and protection from light. The reaction mixture was reducedto a viscous liquid by rotary evaporation and washed with water. Thewashed product was dissolved in ether and water was removed by mixingthe solution with MgSO₄ for 1 hour. The solution was clarified bygravity filtration and the solvent was removed by rotary evaporation.The product (Compound 11′) was re-dissolved in ether, and was purifiedby precipitation through hexane. ¹H NMR (400 MHz, CDCl₃) δ (ppm)6.08-6.17 (vinyl H, HEMA), 5.57-5.64 (vinyl H, HEMA), 4.30-4.54(—CH—O—CONH—, BAL), 4.21-4.27 (—CH—O—CONH—, PCL), 3.99-4.13 (—CH₂—O—,PCL), 3.62-3.77 (minor, CH₃, LDI), 3.09-3.22 (CH ₂—O—CONH—, LDI),2.43-2.56 (CH₂—CF₂, BAL), 2.24-2.40 (O—CO—CH₂—, PCL), 1.92-1.99 (CH3,HEMA), 1.30-1.90 (—CH₂—, PCL).

EXAMPLE 10 Synthesis of α,ω-FEO1-Poly(LDI/PCL) with Pendent Vinyl Groups(Compound 12)

PCL diol (10 g, 8 mmol, degassed) was dissolved in anhydrous DMAc (50mL). LDI (3.39 g, 16 mmol, distilled) and DBDL catalyst was dissolved inanhydrous DMAc (17 mL) and was added dropwise to the PCL diol solution.The pre-polymer reaction was maintained at 60-70° C. for two hours underN₂. FEO1 (9.648 g, 18 mmol) was dissolved in DMAc (24 mL) with DBDL andadded dropwise to the pre-polymer solution. The reactor was kept sealedunder N₂ and stirred overnight at room temperature. The product wasprecipitated in water (3 L) and re-dissolved in chloroform (100 mL, 100ppm BHT), dried with MgSO₄, centrifuged and the supernatant decanted.The chloroform solution was dropped into hexane (400 mL) to precipitatethe product and extract un-reacted reagent. The hexane was decanted andthe solvent extraction procedure was repeated twice. The purifiedproduct (Compound 12) was dissolved in chloroform (50 mL), and thesolvent removed at room temperature in a flow hood. ¹H NMR (400 MHz,CDCl₃) δ (ppm) 6.41-6.49 (FEO1 vinyl H), 6.10-6.21 (FEO1 vinyl H),5.87-5.94 (FEO1 vinyl H), 4.29-4.37 (O—CH₂, FEO1), 4.17-4.27(—CH₂—O—CONH—, PCL, O—CH₂, FEO1), 3.98-4.11 (—CH₂—O—, PCL), 3.73-3.78(CH₃, LDI), 3.64-3.73 (C—H, FEO1) 3.10-3.21 (CH₂—O—CONH—, LDI),2.40-2.58 (CH₂—CF₂, FEO1), 2.26-2.38 (O—CO—CH₂—, PCL), 1.45-1.74 (—CH₂—,PCL), 1.18-1.44 (—CH₂—, PCL). GPC analysis: Compound 12 was dissolved inTHF and run on a GPC system with a polystyrene column and UV detector.No free FEO1 monomer detected in this analysis. IR analysis: 1634 cm⁻¹(C═C).

EXAMPLE 11 Synthesis of α,ω-Allyl-Poly(LDI/PTMO) with Pendent VinylGroups (Compound 13)

PTMO (20.00 g, 23.23 mmol, M_(n)=861 Daltons determined by ¹H-NMR usingpentafluorobenzene as the external reference) was weighed into a 250 mLround bottom flask equipped with a stir bar. The flask was heated to 45°C. using an oil bath, and was held under vacuum for 2 hours to removetrace amounts of water. The flask was removed from the oil bath andallowed to cool to room temperature before LDI (9.86 g, 46.46 mmol) andanhydrous DMAc (100 mL) were transferred to the flask via. two separatesyringes. The reaction flask was heated to 65° C. in the oil bath andDBDL was syringed onto the flask. The reaction mixture was stirred at65° C. for 3 hours, and then cooled to room temperature in an ice bath.Then, liquid allyl alcohol (2.70 g, 46.46 mmoL) was introduced into thereactor by syringe injection, and the reaction mixture was kept stirringat room temperature overnight (17 hours). The next day, the reactionmixture was poured into a 1 L beaker containing 900 mL distilled waterin order to precipitate the polymer. Removing the wash water yielded acrude liquid product. Repeating the washing twice with distilled water(500 mL) generated a slightly yellow liquid. The liquid was dried undera vacuum for 18 hours, and yielded a liquid (Compound 13-ester).Elemental analysis: Theoretical based on reagent stoichiometry (%): C,60.64; H, 9.46; N, 4.00; O, 25.90. Measured: C, 60.52; H, 9.55; N, 3.77;O, 25.36. ¹H-NMR (CDCl₃, 300 MHz): δ 5.92 (CH₂CHCH₂, allyl), 5.25(CH₂CHCH ₂, geminal, allyl), 4.74 (NH), 4.57 (CH ₂CHCH₂, allyl), 4.34(NHCH, LDI), 4.08 (NH(O)COCH ₂, PTMO), 3.74 (—OCH ₃, LDI), 3.42 (OCH₂CH₂CH₂CH ₂O, PTMO), 3.17 (NHCH ₂, LDI), 1.87-1.20 (CHCH ₂CH ₂CH ₂CH₂NH,LDI, and OCH₂CH ₂CHCH₂O, PTMO). Based on integration numbers of LDI at3.17 ppm and allyl at 2.47 ppm, the 5.92 ppm, the amount of allyl groupsattached onto the oligomer after the reaction was estimated to be 71%.The absolute number-average molecular weight (Mn) was estimated, usingpentafluorobenzene (6.90 ppm) as the external reference against allyl at5.92 ppm, PTMO at 3.42 ppm and LDI at 3.17 ppm, to be 1099 g/mol. GPC(DMF, 1 mL/min, linear PS as standards, UV at 280 nm and RI detector).FTIR (KBr, neat): 3315 (N—H, broad), 2933-2794 (aliphatic C—H), 1720(C═O), 1644 (C═C), 1530, 1436, 1365, 1247, 1110, 778, 742 cm⁻¹.

Compound 13-ester (25.0 g, 35.67 mmoL) was weighed in a 500 mL flaskcontaining 150 mL MeOH (HPLC grade) and a stir bar. A base solution of1.62 g (40.5 mmoL) solid NaOH dissolved in 4.20 g of distilled water wasadded dropwise to the flask and the mixture was stirred at roomtemperature for 18 hours. The next day, the reaction mixture wasneutralized with 7.0 mL of 6.0 N aqueous HCl, and then poured into a 2 Lbeaker containing 1.4 L distilled water, to yield a white precipitate.Extracting organic soluble materials (includes the desired product) intodiethyl ether solvent, drying the organic solvent over solid MgSO₄, andremoving the solvent by rotary evaporator at room temperature yielded aclear liquid. The organic solvent was further dried under vacuum for 18hours to yield a clear viscous product, Compound 13-acid. Elementalanalysis: Theoretical based on reagent stoichiometry (%): C, 60.13; H,9.36; N, 4.08; O, 26.46. Measured: C, 60.05; H, 9.58; N, 3.36; O, 25.64.¹H-NMR (CDCl₃, 300 MHz): δ 5.92 (CH₂CHCH₂, allyl), 5.25 (CH₂CHCH ₂,geminal, allyl), 4.74 (NH), 4.57 (CH ₂CHCH₂, allyl), 4.34 (NHCH, LDI),4.08 (NH(O)COCH ₂, PTMO), 3.42 (OCH ₂CH₂CH₂CH ₂O, PTMO), 3.17 (NHCH ₂,LDI), 1.87-1.20 (CHCH ₂CH ₂CH ₂CH₂NH, LDI, and OCH₂CH ₂CH ₂CH₂O, PTMO).The singlet at 3.74 (—OCH₃) disappeared almost completely, confirmingthe hydrolysis of the ester group. Based on the peak integration theestimated conversion of ester to acid group was 97%. FTIR (KBr, neat):3315 (N—H, broad), 2933-2794 (aliphatic C—H), 1720 (C═O), 1644 (C═C),1530, 1436, 1365, 1247, 1110, 778, 742 cm⁻¹.

EXAMPLE 12 Synthesis of α,ω-C8-Poly(LDI(HEMA)/PTMO) with Pendent VinylGroups (Compound 15)

PTMO (41.29 g, 40.01 mmol, Mn=1032 Daltons, determined by titration ofhydroxyl groups) was weighed into a 250 mL round bottom flask equippedwith a stir bar. The flask was heated to 45° C. using an oil bath, andwas held under vacuum for 2 hours to remove trace amounts of water. Theflask was removed from the oil bath and allowed to cool to roomtemperature before LDI (16.97 g, 80.02 mmol) and anhydrous DMAc (100 mL)were transferred to the flask via. two separate syringes. The reactionflask was heated to 65° C. in the oil bath and DBDL (0.05 mL) wassyringed into the flask. The reaction mixture was stirred at 65° C. for3 hours. Then, 1-octanol (10.42 g, 80.02 mmoL) was introduced into thereactor by syringe injection, and the reaction mixture was kept stirringat 65° C. overnight (17 hours). The next day, the reaction mixture wascooled to room temperature and poured into a 1 L beaker containing 900mL distilled water in order to precipitate the polymer. Removing thewash water yielded a crude liquid product. Repeating the washing twicewith distilled water (500 mL) generated a slightly yellow liquid(Compound 14-ester). The liquid was dried under a vacuum for 18 hours,and yielded a liquid with increased viscosity. Elemental analysis:Theoretical, based on reagent stoichiometry (%): C, 63.13; H, 10.24; N,3.26; O, 23.36. Measured: C, 62.28; H, 10.13; N, 3.33; O, 24.19. ¹H-NMR(CDCl₃, 300 MHz): δ 5.23 (NH), 4.72 (NH), 4.34 (NHCH, LDI), 4.08(NH(O)COCH ₂, PTMO), 3.74 (—OCH ₃, LDI), 3.42 (OCH ₂CH₂CH₂CH ₂O, PTMO,and (O)COCH(CH₂)₆CH₃, octanol), 3.17 (NHCH ₂, LDI), 1.84-1.18 (CHCH ₂CH₂CH ₂CH₂NH, LDI, OCH₂CH ₂CH ₂CH₂O, PTMO, and (O)COCH₂(CH ₂)₆CH₃,octanol), 0.89 ((O)COCH₂(CH₂)₆CH ₃, octanol). Based on integrationnumbers of LDI at 3.17 ppm and octanol at 0.89 ppm, the amount ofoctanol attached onto the oligomer after the reaction was estimated tobe 89%. The absolute number-average molecular weight (Mn) was estimated,using pentafluorobenzene (6.90 ppm) as the external reference againstoctanol at 0.89 ppm, PTMO at 3.42 ppm and LDI at 3.17 ppm, to be 1425g/mol. FTIR (KBr, neat): 3314 (N—H, broad), 2933-2728 (aliphatic C—H),1710 (C═O), 1524, 1437, 1364, 1245, 1238, 1204, 1107, 778 cm⁻¹.

Compound 14-ester (45.0 g, 52.4 mmoL) was weighed in a 500 mL flaskcontaining 150 mL MeOH (HPLC grade) and a stir bar. A base solution of2.31 g (57.7 mmoL) solid NaOH dissolved in 6 g of distilled water wasadded dropwise to the flask and the mixture was stirred at roomtemperature for 21 hours. The next day, the reaction mixture wasneutralized with 11.0 mL of 6.0 N aqueous HCl, and then poured into a 2L beaker containing 1.4 L distilled water, to yield a white precipitate.Once the wash water was removed, a crude waxy product was obtained. Thiswas washed twice with distilled water (1.0 L), and the final product wasdried under vacuum for 18 hours to yield an opaque viscous product(Compound 14-acid). Elemental analysis: Theoretical, based on reagentstoichiometry (%): C, 62.76; H, 10.18; N, 3.32; O, 23.74. Measured: C,62.08; H, 10.15; N, 3.32; O, 23.19. ¹H-NMR (CDCl₃, 300 MHz): δ δ 5.23(NH), 4.72 (NH), 4.34 (NHCH, LDI), 4.08 (NH(O)COCH ₂, PTMO), 3.42 (OCH₂CH₂CH₂CH ₂O, PTMO, and (O)COCH ₂(CH₂)₆CH₃, octanol), 3.17 (NHCH ₂,LDI), 1.84-1.18 (CHCH ₂CH ₂CHCH₂NH, LDI, OCH₂CH ₂CH ₂CH₂O, PTMO, and(O)COCH₂(CH ₂)₆CH₃, octanol), 0.89 ((O)COCH₂(CH₂)₆CH ₃, octanol). Thesinglet at 3.74 (—OCH₃) disappeared, confirming the hydrolysis of theester group. Based on the peak integration the estimated conversion ofester to acid group was 81%. The absolute number-average molecularweight (Mn) was estimated, using pentafluorobenzene (6.90 ppm) as theexternal reference against octanol at 0.89 ppm, PTMO at 3.42 ppm and LDIat 3.17 ppm, to be 1430 g/mol. FTIR (KBr, neat): 3314 (N—H, broad),2933-2728 (aliphatic C—H), 1710 (C═O), 1524, 1437, 1364, 1245, 1238,1204, 1107, 778 cm⁻¹.

Compound 14-acid (12.20.0 g, 14.45 mmol), DMAP (0.88 g, 7.23 mmoL), HEMA(11.28 g, 86.70 mmol) and anhydrous DCM (150 g) were weighed into a 250mL flask equipped with a stir bar. The contents of the flask weremagnetically stirred until all ingredients were dissolved. Then EDC(8.31 g, 43.35 mmol) was added to the flask. The reaction flask waswrapped with aluminium foil and the solution was stirred at roomtemperature under N₂ for 5 days. After 5 days, DCM was removed by rotaryevaporator at 25° C. to yield a viscous crude product. The crude productwas washed three times with aqueous HCl (each time using a mixture of 30mL of 0.1N HCl and 60 mL distilled water), and finally with distilledwater (100 mL) itself. Extracting organic soluble materials (includesthe desired product) into diethyl ether solvent, drying the organicsolvent over solid MgSO₄, and removing the solvent by rotary evaporatorat room temperature yielded a slightly yellow liquid. Columnchromatography of the viscous liquid using first diethyl ether, adiethyl ether/DCM mixture (50/50, w/w), DCM itself, and then a DCM/MeOHmixture (70/30, w/w) yielded a clear viscous liquid (Compound 15), 6.35g (46%). Elemental analysis: Theoretical, based on reagent stoichiometry(%): C, 62.95; H, 9.83; N, 2.93; O, 24.31. Measured: C, 62.17; H, 9.84;N, 3.18; O, 24.11. ¹H-NMR (CDCl₃, 300 MHz): δ 6.12 (geminal CH, HEMA),5.60 (geminal CH, HEMA), 5.24 (NH), 5.23 (NH), 4.77 (NH), 4.34 (NHCH,LDI, and OCH ₂CH ₂O, HEMA), 4.08 (NH(O)COCH ₂, PTMO), 3.51-3.30 (OCH₂CH₂CH₂CH ₂O, PTMO, and (O)COCH ₂(CH₂)₆CH₃, octanol), 3.14 (NHCH ₂,LDI), 1.95 ((O)CC(CH ₃)CH₂, HEMA), 1.84-1.18 (CHCH ₂CH ₂CH ₂CH₂NH, LDI,OCH₂CH ₂CH ₂CH₂O, PTMO, and (O)COCH₂(CH ₂)₆CH₃, octanol), 0.89((O)COCH₂(CH₂)₆CH ₃, octanol). The estimate conversion of COOH toCO-HEMA is 48% based on ¹H-NMR shift area of 6.12 ppm (HEMA) and 3.14ppm (LDI). The absolute number-average molecular weight (Mn) wasestimated, using pentafluorobenzene (6.90 ppm) as the external referenceagainst octanol at 0.89 ppm, PTMO at 3.42 ppm and LDI at 3.17 ppm, to be1722 g/mol. GPC analysis: the product was dissolved in dioxane and runon a GPC system with a polystyrene column and UV detector: no freemonomer was detected. HPLC analysis: retention time of 41 minutes(Compound 15), no free monomer detected. Reversed phase HPLC, C18column, MeOH and pH 9 PBS mobile phase (gradient). FTIR (KBr, neat):3314 (N—H, broad), 2933-2728 (aliphatic C—H), 1710 (C═O), 1636 (C═C),1524, 1437, 1364, 1245, 1238, 1204, 1107, 778 cm⁻¹.

EXAMPLE 13 Synthesis of α,ω-C8-Poly(LDI(Allyl)/PTMO) with Pendent VinylGroups (Compound 16)

Compound 14-acid (9.83 g, 11.64 mmol), DMAP (0.71 g, 5.82 mmol), allylalcohol (4.06, 69.86 mmol) and anhydrous DCM (100 g) were weighed into a250 mL flask equipped with a stir bar. The contents of the flask weremagnetically stirred until all ingredients were dissolved. Then EDC(6.70 g, 34.93 mmol) white solid was added to the flask. The reactionflask was wrapped with aluminium foil and the solution was stirred atroom temperature under N₂ for 3 days. After 3 days, DCM was removed byrotary evaporator at 25° C. to yield a viscous crude product. The crudeproduct was washed three times with aqueous HCl (each time using amixture of 30 mL of 0.1N HCl and 60 mL distilled water), and finallywith distilled water (100 mL) itself. Extracting organic solublematerials (includes the desired product) into diethyl ether solvent,drying the organic solvent over solid MgSO₄, and removing the solvent byrotary evaporator at room temperature yielded a clear liquid. Columnchromatography of the viscous liquid using first diethyl ether, adiethyl ether/DCM mixture (50/50, w/w), DCM itself, and then a DCM/MeOHmixture (70/30, w/w) yielded a clear viscous product (Compound 16), 6.21g (60% yield). Elemental analysis: Theoretical based on reagentstoichiometry (%): C, 63.99; H, 10.17; N, 3.17; O, 22.67. Measured: C,62.51; H, 9.97; N, 3.19; O, 24.01. ¹H-NMR (CDCl₃, 300 MHz): δ 5.92(CH₂CHCH₂, allyl), 5.28 (CH₂CHCH ₂ (geminal, allyl)), 4.74 (NH), 4.64(CH ₂CHCH₂, allyl), 4.35 (NHCH, LDI), 4.08 (NH(O)COCH ₂, PTMO), 3.42(OCH ₂CH₂CH₂CH ₂O, PTMO, and (O)COCH ₂(CH₂)₆CH₃, octanol), 3.15 (NHCH ₂,LDI), 1.84-1.18 (CHCH ₂CH ₂CH ₂CH₂NH, LDI, OCH₂CH ₂CH ₂CH₂O, PTMO, and(O)COCH₂(CH ₂)₆CH₃, octanol), 0.89 ((O)COCH₂(CH₂)₆CH ₃, octanol). Theestimate conversion of COOH to CO-allyl alcohol is 38% based on ¹H-NMRshift area of 5.92 ppm (allyl) and 3.15 ppm (LDI). The absolutenumber-average molecular weight (Mn) was estimated, usingpentafluorobenzene (6.90 ppm) as the external reference against octanolat 0.89 ppm, allyl at 5.92 ppm, PTMO at 3.42 ppm and LDI at 3.17 ppm, tobe 1576 g/mol. GPC analysis: the product was dissolved in dioxane andrun on a GPC system with a polystyrene column and UV detector: no freemonomer was detected. HPLC analysis: retention time of 41 minutes(Compound 16), no free monomer detected. Reversed phase HPLC, C18column, MeOH and pH 9 PBS mobile phase (gradient). FTIR (KBr, neat):3314 (N—H, broad), 2933-2728 (aliphatic C—H), 1710 (C═O), 1650 (C═C),1524, 1437, 1364, 1245, 1238, 1204, 1107, 778 cm⁻¹.

Cured System Based on Homo Cross-Linking EXAMPLE 14 Homo Cross-LinkedFilms of Compound 2 Prepared by UV Cure in Air

Compound 2 (0.50 g) and HMP (0.0025 g) were weighed a 20 mL vial. Asmall amount of MeOH (HPLC grade, 0.3 g) was added to the vial to reducethe viscosity of the mixture and to ensure good mixing. The vial wasvortexed until the components were completely well blended. The mixturewas cast onto various substrates including stainless steel discs orplates, an aluminum weighing pan and a KBr disc. MeOH solvent wasallowed to evaporate at room temperature for 1 h under an aluminum foil.The stainless steel substrates, weighing pan and KBr disc containingliquid samples were placed in the center of the UV box before the UVlamp was turned on for 5 minutes, to yield the solid polymer films. Allsubstrates were removed from the box and cooled to room temperaturebefore carrying out film analysis.

Gel content, swell ratio, contact angle measurements, DSC and TGAanalysis were performed on films prepared on stainless steel substrates.The typical thickness of these films was 0.4 mm. XPS analysis wasperformed on films cast in weighing pans. Gel content: 98%±3 (n=3).Swell ratio: 1.6±0.2 (n=3). Contact angle: 131.0°±2.7 (5 spots, 3measurements/spot). XPS analysis (90°): (top surface: C: 68.84%, N:4.08%, O:14.24%, F:28.44%.) DSC: negative heat flow: −70.34° C. (T_(g)of PTMO). TGA: 2 onset points: (A) 259.1° C., 28.3% mass loss, and (B)404.9° C., 69.4% mass loss. The C═C group conversion was monitored onfilms prepared on KBr discs: C═C conversion was recorded.

EXAMPLE 15 Homo Cross-Linked Films of Compound 2 Prepared by UV CureUnder Argon with Two Different Concentrations of Initiator (0.5 and 1 wt%)

Compound 2 (2.9815 g or 2.9542 g) and HMP (0.0145 g or 0.0298 g) wereweighed in a 20 mL vial. MeOH (HPLC grade, 5 g) was added to the vial toreduce the viscosity of the mixture and to ensure good mixing. The vialwas vortexed until the components were completely well blended. If airbubbles appeared, the vial was allowed to sit at room temperature untilall bubbles dissipated, before the mixture was cast onto the desiredsubstrates such as Teflon molds, stainless steel discs, an aluminumweighing pan and a KBr disc. MeOH solvent was allowed to evaporate atroom temperature for 1 hour or 24 hours under an aluminum foil. After 1hour, the stainless steel discs, aluminum weighing pan and KBr disccontaining liquid samples were placed in the center of the UV box. Thebox was purged with argon gas for 10 minutes before the UV lamp wasturned on for 5 minutes. All substrates were removed from the box andcooled to room temperature before carrying out film analysis. After 24hours, the UV cure procedure was repeated to samples cast on Teflonmolds. Gel content, swell ratio, contact angle measurements, TGAanalysis were performed on films prepared on stainless steel discs. Thetypical thickness of these films was 0.4 mm. XPS analysis was performedon films cast in weighing pans. The C═C group conversion was monitoredby FTIR and performed on films prepared on KBr discs. The averagethickness of these latter two films was about 0.03 mm. For tensilemeasurements, transparent polymer films free of air bubbles were removedfrom the molds and cut into to dog-bone shape (FIG. 1). The dog-bonesamples were air-tightened on an instron machine for subsequent tensiletest measurements. An Instron 4301 system was used to test the sampleswith a cross-head load of 50 N at the rate of 10 mm/min, at 23° C. andrelative humidity of 57%. Sample thickness was measured by a caliperranged from 0.1 to 0.3 mm. The results of each example represent anaverage of 4 or 5 dog-bone samples.

TABLE 2 Polymer film properties after Compound 2 was UV cured with 0.5and 1.0 wt % photoinitiator under an inert atmosphere. 0.5 wt %photoinitiator 1.0 wt % photoinitiator C = C conver- Recorded Recordedsion (%) Gel content (%)   98 ± 3 (n = 3)   97 ± 1 (n = 3) Swell ratio 1.43 ± 0.05 (n = 3)  1.41 ± 0.04 (n = 3) Contact angle 133.4 ± 2.2132.4 ± 2.2 (°) XPS (90°) C: 53.39%, N: 4.24%, C: 52.03%, N: 4.06%, O:14.15%, F: 28.12%. O: 14.17%, F: 29.50%. TGA 265.1° C., 27.8% mass loss251.7° C., 18.2% mass loss 412.9° C., 69.6% mass loss 401.9° C., 75.9%mass loss Tensile testing n = 3 n = 3 Stress at break: 3.0 MPa Stress atbreak: 2.9 MPa Strain at break: 41% Strain at break: 37.5% Initialmodulus (10% Initial modulus (10% strain): 0.084 strain): 0.085Toughness: 66.4 MPa Toughness: 61.6 MPa

EXAMPLE 16 Homo Cross-Linked Films of Compound 3 Prepared by UV Cure

Compound 3 (0.5934 g), HMP (0.0029 g) and MeOH (HPLC grade, 0.3 g) wereweighed in a 20 mL vial. The vial was vortexed until all the componentswere well blended. If air bubbles appeared, the vial was allowed to sitat room temperature until all bubbles dissipated, before the mixture wascast onto the desired substrates (stainless steel discs, an aluminumweighing pan and a KBr disc). MeOH solvent was allowed to evaporate atroom temperature for 1 h under an aluminum foil. The stainless steeldiscs, aluminum weighing pan and KBr disc containing liquid samples wereplaced in the center of the UV box. The box was purged with argon gasfor 10 minutes before the UV lamp was turned on for 5 minutes. Allsubstrates were removed from the box and cooled to room temperaturebefore carrying out film analysis. Gel content, swell ratio, contactangle measurements, DSC and TGA analysis were performed on filmsprepared on stainless steel disks. The typical thickness of these filmswas 0.4 mm. XPS analysis was performed on films cast in aluminumweighing pans. The C═C group conversion was monitored by FTIR, andperformed on films prepared on KBr disks. The average thickness of thelatter two films was about 0.03 mm. Gel content: 56.3% Contact angle:spread and detached in about 4.5 minutes, with an average angle ofdetached droplet=71°. DSC: negative heat flow −67° C. TGA: 2 onsetpoints: (A) 240.8° C., 34.09% mass loss, (B) 417.5° C., 62.99% massloss. XPS: C: 56.2%, N: 3.80%, O: 14.14%, F: 25.79%.

EXAMPLE 17 Homo Cross-Linked Films of Compound 4 Prepared by UV Cure

Compound 4 (0.4056 g) and HMP (0.0022 g) were weighed in a 20 mL vial. Asmall amount of MeOH (HPLC grade, 0.3 g) was added to the vial to reducethe viscosity of the mixture and to ensure good mixing. The vial wasvortexed until all components were well mixed. The mixture was cast ontovarious substrates including stainless steel discs, an aluminum weighingpan and a KBr disc. MeOH solvent was allowed to evaporate at roomtemperature for 1 h under an aluminum foil. The stainless steelsubstrates, aluminum weighing pans and KBr disc containing opaque liquidsamples were placed in the center of the UV box. The box was purged withargon gas for 10 minutes before the UV lamp was turned on for 5 minutes.All substrates were removed from the box and cooled to room temperaturebefore carrying out film analysis. Gel content, swell ratio, contactangle measurements, DSC and TGA analysis were performed on filmsprepared on stainless steel discs. The typical thickness of these filmswas 0.4 mm. XPS analysis was performed on films cast in aluminumweighing pans. The C═C group conversion was monitored by FTIR, andperformed on films prepared on KBr disks. The average thickness of thelatter two films was about 0.03 mm. Gel extraction analysis (acetone):56.3% gel, 550% swelling. Contact angle: Spreading as water dropletcontact the surface and detached from the needle in about 1 minute. DSC:negative heat flow −68° C. TGA: 2 onset points: (A) 288.4° C., 31.4%mass loss, (B) 411.8° C., 67.2% mass loss. XPS: C: 58.31%, N: 2.86%, O:15.97%, F: 21.89%.

EXAMPLE 18 Homo Cross-Linked Films of Compound 10 Prepared by UV Cure

Compound 10 (3.9782 g) and HMP (0.0191 g) were weighed in a 20 mL vial.DCM (6 g) was added to the vial to reduce the viscosity of the mixtureand to ensure good mixing. The vial was vortexed until all componentswere well mixed. The solution appeared transparent. If air bubblesappeared, the vial was allowed to sit at room temperature until allbubbles dissipated, before the mixture was cast onto the desiredsubstrates such as Teflon molds, stainless steel discs, an aluminumweighing pan and a KBr disc. DCM solvent was allowed to evaporate atroom temperature for 1 hour or 24 hours under an aluminum foil. After 1hour, the stainless steel discs, aluminum weighing pan and KBr disccontaining liquid samples were placed in the center of the UV box.Samples appeared transparent. The box was purged with argon gas for 10minutes before the UV lamp was turned on for 5 minutes. All substrateswere removed from the box and cooled to room temperature before carryingout film analysis. After 24 hours, the UV cure procedure was repeatedfor samples cast on Teflon molds. Film characteristics were recorded.

EXAMPLE 19 Homo Cross-Linked Films of Compound 2 Prepared by Heat Curewith a Range of BPO Initiator Concentration

A range of BPO concentrations (0, 0.05, 0.1, 0.5, and 1 wt % BPO) wereevaluated for effectiveness of cure of Compound 2. Compound 2 wasdissolved in toluene (0.1 g/mL) prepared with BPO (0, 0.05, 0.1, 0.5,and 1 wt %). 500 μL of these solutions were cast into 4 mL glass vials,the toluene was evaporated off at room temperature, and the films werecured at 60° C. in an N₂ purged oven. Films prepared with 0, 0.05, and0.1 wt % BPO content did not cure enough to permit physicalmanipulation. Films prepared with 0.5 and 1 wt % BPO were analyzed forgel content (acetone extraction): 1 wt % BPO film (100% gel), 0.5 wt %BPO film (58% gel). Equivalent films were also prepared on KBr disksusing 25 μL of the polymer solutions, and these films were analyzed byFTIR. The films prepared with 0-0.1 wt % BPO have signal at 1634 cm⁻¹(C═C peak), whereas films prepared with 0.5 and 1 wt % BPO have novisible 1634 cm⁻¹ signal.

Larger films of Compound 2 with 1 wt % BPO initiator were prepared forfurther analysis. Compound 2 was dissolved in toluene (0.1 g/mL)containing BPO initiator (1 mg, 1 wt % of Compound 2 mass). The toluenesolution was cast into a 4 cm×4 cm PTFE wells (6 mL per well), and thePTFE casting plate was placed in a semi-enclosed chamber at roomtemperature for 1 day. The Compound 2 films were then cured for 12 hoursin an N₂ purged 60° C. oven. The resulting films were clear andelastomeric (FIG. 2). Gel extraction analysis (acetone): 95% gel, 129%swelling. Contact angle analysis: water: 118°, porcine plasma: 113°,porcine blood: 121°. XPS analysis (90°): (top surface: C: 41.4%, N:1.1%, O: 9.9%, F: 45.4%.) (bottom surface: C: 46.3%, N: 2.2%, O: 11.1%,F: 39.5%). DSC analysis: Tg=−69° C. TGA analysis: decomposition onset at174° C.

Films of Compound 2 were prepared with 1 wt % V-70 initiator, and werecured in the same manner as the BPO cured film. By DSC analysis, theV-70 was found to be an effective initiator.

Shaped articles of Compound 2 were prepared. Compound 2 was dissolved intoluene (0.1 g/mL) containing BPO initiator (1 mg, 1 wt % of Compound 2mass). The toluene solution was cast into circular and hexagonal molds,and the molds were placed in a semi-enclosed chamber at room temperaturefor 1 day. The Compound 2 films were then cured for 12 hours in an N₂purged 60° C. oven. The resulting shaped articles could be removed fromthe molds, and were elastomeric (FIG. 3).

EXAMPLE 20 Homo Cross-Linked Films of Compound 6 Prepared by Heat Cure

Compound 6 was dissolved in toluene (0.1 g/mL) prepared with BPO (0,0.05, 0.1, 0.5, and 1 wt %). 1.5 mL of each solution were cast into 24mL glass vials, the toluene was evaporated off at room temperature, andthe films were cured at 60° C. in an N₂ purged oven. All films exceptingthe 0% BPO film were firm and clear. The film prepared with 0% BPO wassoft and tacky. Gel content (acetone extraction): 0 wt % BPO film(completely dissolved), 0.05, 0.1, 0.5 and 1 wt % BPO films (>99% gel).The acetone extraction solutions were reduced to dryness, and analyzedby ¹H NMR (400 MHz, CDCl₃): all extractions had NMR signaturesconsistent with the Compound 6 spectra. The 0 and 0.05 wt % BPO filmextraction spectra contained vinyl signals (5.80-6.40 ppm) consistentwith un-cured Compound 6, whereas the remaining extraction spectra didnot show evidence of vinyl chemistry. Extractions of films containingBPO also had weak signals at 7.1 and 8.1 ppm, suggestive of the BPOinitiator. Cured films were also prepared on KBr disks using 25 μL ofthe above polymer solutions, and these films were analyzed by FTIR.

Larger films of Compound 6 with 1 wt % BPO were prepared for furtheranalysis. Compound 6 films were prepared using 1 wt % BPO. Compound 6was dissolved in toluene (0.05 or 0.1 g/mL) containing BPO initiator (1wt % of Compound 6). The toluene solutions (6 mL) were cast into 4 cm×4cm PTFE wells, and the PTFE casting plates were placed in a casting tankat room temperature for 1 day. The Compound 6 films were cured for 12hours in an N₂ purged 60° C. oven. The resulting films were clear andelastomeric (FIG. 4). Gel content of 0.1 g/mL films (acetoneextraction): 96% gel, 126% swelling. Gel content of 0.05 mg/mL films(toluene extraction): 92% gel, 193% swelling. Gel content of 0.1 mg/mLfilms (toluene extraction): >99% gel, 180% swelling. FIG. 5 shows filmsof cured Compound 6 prepared using the 0.05 and 0.1 g/mL solutions,before and after toluene exposure, indicating no change to filmmorphology. Contact angle analysis: water: 114°, porcine plasma: 119°,porcine blood: 116°. XPS analysis (90°): (top surface: C: 56.5%, N:2.6%, O: 16.4%, F: 23.7%.) (bottom surface: C: 52.6%, N: 2.4%, O: 14.0%,F: 30.3%). DSC analysis: T_(g)=−65° C. TGA analysis: decomposition onsetat 200° C. Tensile testing: stress at break=2.4 MPa, strain atbreak=42%. Films of Compound 6 were also prepared with 1 wt % V-70initiator, and were cured in the same manner as the BPO cured film. ByDSC analysis, the V-70 was found to be an effective initiator.

EXAMPLE 21 Homo Cross-Linked Films of Compound 8 Prepared by Heat Cure

Compound 8 was dissolved in toluene (0.1 gram/mL) containing BPO (1 wt %of Compound 8). The toluene solution (6 mL) was cast into 4 cm×4 cm PTFEwells, and the PTFE casting plate was placed in a casting tank at roomtemperature for 1 day. The Compound 8 films were cured for 12 hours inan N₂ purged 60° C. oven. The resulting films were clear, tacky, andelastomeric. Gel extraction analysis: 91% gel, 117% swelling. Contactangle analysis: advancing angle: 119°. XPS analysis (90°): (top surface:C: 59.9%, N: 2.8%, O: 17.5%, F: 19.8%.) (bottom surface: C: 58.0%, N:2.5%, O: 16.3%, F: 23%). Tensile testing: stress at break=1.5 MPa,strain at break=35%. Films of Compound 8 were also prepared with 1 wt %V-70 initiator, and were cured in the same manner as the BPO cured film.By DSC analysis, the V-70 was found to be an effective initiator.

EXAMPLE 22 Homo Cross-Linked Films of Compound 12 Prepared by Heat Cure

Compound 12 was dissolved in THF (0.1 gram/mL) containing BPO (1 wt % ofCompound 12). The THF solution (6 mL) was cast into 4 cm×4 cm PTFEwells, and the PTFE casting plate was placed in a casting tank at roomtemperature for 1 day. The Compound 12 films were cured for 12 hours inan N₂ purged 60° C. oven. The resulting films were translucent andelastomeric (FIG. 6). Gel extraction analysis (acetone): 97% gel, 136%swelling. Contact angle analysis: advancing angle: 118°. XPS analysis(90°): (top surface: C: 50.6%, N: 1.9%, O: 14.5%, F: 32.8%.) (bottomsurface: C: 49.7%, N: 1.7%, O: 13.3%, F: 35.3%). Tensile testing: stressat break=2.0 MPa, strain at break=33%.

Cured System Based on Hertero Cross-Linking EXAMPLE 23 HeteroCross-Linked Films of Blended Compound 2 and Compound 15, Prepared by UVCure

Compound 2 (2.0311 g), Compound 15 (2.0345 g) and HMP (0.0195 g) wereweighed in a 20 mL vial. MeOH (HPLC grade, 5 g) was added to the vial toreduce the viscosity of the mixture and to ensure good mixing. The vialwas vortexed until the compounds were all very well mixed. If airbubbles appeared, the vial was allowed to sit at room temperature untilall bubbles dissipated, before the mixture was cast onto the desiredsubstrates (Teflon molds, stainless steel discs, an aluminum weighingpan and a KBr disc). The solution appeared transparent. MeOH solvent wasallowed to evaporate at room temperature for 1 hour and 24 hours underan aluminum foil. All films appeared opaque. The stainless steelsubstrates, aluminum weighing pans and KBr disc containing opaque liquidsamples were placed in the center of the UV box. The box was purged withargon gas for 10 minutes before the UV lamp was turned on for 5 minutes.All substrates were removed from the box and cooled to room temperaturebefore carrying out film analysis. After 24 hours, the UV cure procedurewas repeated to samples cast on Teflon molds. Gel content, swell ratio,contact angle measurements, and TGA analysis were performed on filmsprepared on stainless steel discs. The typical thickness of these filmswas 0.4 mm. XPS analysis was performed on films cast in aluminumweighing pans. The C═C group conversion was monitored by FTIR, andperformed on films prepared on KBr disc. The average thickness of theselatter two films was about 0.03 mm. For tensile measurements, opaquepolymer films free of air bubbles were removed from the molds and cutinto to dog-bone shape. The dog-bone samples were air-tightened on aninstron machine for subsequent tensile test measurements. An Instron4301 system was used to test the samples with a cross-head load of 50 Nat the rate of 10 mm/min, at 23° C. and relative humidity of 57%. Samplethickness measured by a caliber ranged from 0.1 to 0.3 mm. The resultsof each example represented an average of 5 dog-bone samples.

TABLE 3 Comparison of film properties prepared from a blend of Compound2 and Compound 15 to films prepared from Compound 15 itself.Photoinitiator concentration in both systems was kept at 0.5 wt %. Blendof Compound 2 and Compound 15 Compound 15 C = C conversion (%) RecordedRecorded Gel content (%) 83 88 Contact angle (°) From 138 down to 75 in5 104.1 ± 2.8 minutes. Remained intact after 5 minutes XPS C: 51.45%, N:4.56%, C: 52.89%, N: 3.47%, O: 11.92%, F: 31.98%. O: 21.55%, F: 0%. DSCT_(g) = −68.70° C. T_(g) = −67.37° C. TGA 264.1 °C., 20% mass loss273.8° C., 12% mass 411.4° C., 75% mass loss loss 406.9° C., 84% massloss Tensile testing Stress at break = 1.4 MPa Stress at break = 1.2Strain at break = 32.3% MPa Strain at break = 36.5%

EXAMPLE 24 Hetero Cross-Linked Films of Blended Compound 2 and Compound10, Prepared by UV Cure

Compound 10 (1.9639 g), Compound 2 (2.0037 g), and HMP (0.0221 g) wereweighed in a 20 mL vial. DCM (5 g) was added to the vial and the vialwas vortexed until all components were well dissolved. The solutionappeared translucent and exhibited phase separating. Diethyl ether (4 g)was then added to the vial, and the vial was vortexed and allowed to sitat room temperature. Again, phase separation occurred, The mixture wascast onto the desired substrates such as Teflon molds, stainless steeldiscs, an aluminum weighing pan and a KBr disc. DCM and diethyl ethersolvents were allowed to evaporate at room temperature for 1 hour or 24hours under an aluminum foil. After 1 hour, the stainless steel discs,aluminum weighing pan and KBr disc containing liquid samples were placedin the center of the UV box. Samples on all substrates appeared clearwith visual droplets. The box was purged with argon gas for 10 minutesbefore the UV lamp was turned on for 5 minutes. All substrates wereremoved from the box and cooled to room temperature before carrying outfilm analysis. After 24 hours, the UV cure procedure was repeated forsamples cast on Teflon molds.

EXAMPLE 25 Hetero Cross-Linked Films of Blended Compound 2 and VinylPyrrolidone, Prepared by UV Cure

Compound 2 (2.9929 g), vinyl pyrrolidone (0.9822 g), HMP (0.0191 g) andMeOH (HPLC grade, 5 g) were weighed in to a 20 mL vial. The vial wasvortexed until all contents was well mixed. If air bubbles appeared, thevial was allowed to sit at room temperature until all bubbles dissipatedbefore the mixture was cast on Telfon molds, stainless steel substrates,an aluminum weighing pan and a KBr disc. MeOH solvent was allowed toevaporate at room temperature for 1 hour or 24 hours under an aluminumfoil. After 1 hour, the stainless steel discs, aluminum weighing pan andKBr disc containing liquid samples were placed in the center of the UVbox. The box was purged with argon gas for 10 minutes before the UV lampwas turned on for 5 minutes. All substrates were removed from the boxand cooled to room temperature before carrying out film analysis. After24 hours, the UV cure procedure was repeated to samples cast on Teflonmolds. Gel content, swell ratio, contact angle measurements and TGAanalysis were performed on films prepared on the stainless steelsubstrates. The typical thickness of these films was 0.4 mm. XPSanalysis was performed on films cast on aluminum weighing pans (0.03 mmthick). Gel extraction analysis: 85% gel, 180% swelling. Contact angle:134.5°±2.1. TGA: 2 onset points: (A) 293.2° C., 25.9% mass loss, (B)418.2° C., 68.5% mass loss. FTIR analysis: the elimination of the C═Cgroup was monitored to observe the polymerization of the materialsprepared on the KBr disc. Tensile testing: stress at break=7.3 MPa,strain at break=69.8%. XPS analysis (90°): C: 47.65%, N: 3.45%, O:10.53%, F: 38.42%.

EXAMPLE 26 Hetero Cross-Linked Films of Blended Compound 2 and HEMA,Prepared by UV Cure

Compound 2 (0.4003 g), HEMA (0.1485 g) and HMP (0.0033 g) were weighedin to a 20 mL vial. The vial was vortexed until Compound 2 wascompletely dissolved. If air bubbles appeared, the vial was allowed tosit at room temperature until all bubbles dissipated, before the mixturewas cast onto the desired substrates (stainless steel discs, an aluminumweighing pan and a KBr disc). The stainless steel substrates, weighingpans and KBr disc containing liquid samples were placed in the center ofthe UV box. The box was purged with argon gas for 10 minutes before theUV lamp was turned on for 5 minutes. All substrates were removed fromthe box and cooled to room temperature before carrying out filmanalysis. Gel content, swell ratio, contact angle measurements and TGAanalysis were performed on films prepared on the stainless steelsubstrates. The typical thickness of these films was 0.4 mm. XPSanalysis was performed on films cast on aluminum weighing pans (0.03 mmthick). Gel extraction analysis: 90.3% gel, 192% swelling. Contactangle: The water droplet spread quickly on the film surface and detachedfrom the needle in about 1 minute. The contact angle of the detacheddroplet is about 65°±2 (n=3). DSC: T_(g)=10.3° C. TGA: 2 onset points:(A) 299.4° C., 27.8% mass loss, (B) 414.7° C., 66.1% mass loss. IR: theC═C group conversion was monitored by FTIR and performed on filmsprepared on the KBr disc. XPS analysis (90°): C: 50.94%, N: 3.38%, O:11.41%, F: 34.27%.

EXAMPLE 27 Hetero Cross-Linked Films of Blended Compound 2 andMethacrylic Acid, Prepared by UV Cure

Compound 2 (0.4047 g), MAA (0.1321 g) and HMP (0.0035 _(g)) were weighedin to a 20 mL vial. The vial was vortexed until Compound 2 wascompletely dissolved. If air bubbles appeared, the vial was allowed tosit at room temperature until all bubbles dissipated, before the mixturewas cast onto desired substrates (stainless steel discs, an aluminumweighing pan and a KBr disc). The stainless steel substrates, aluminumweighing pan and KBr disc containing liquid samples were placed in thecenter of the UV box. The box was purged with an argon gas for 10minutes before the UV lamp was turned on for 5 minutes. All substrateswere removed from the box and cooled to room temperature before carryingout film analysis. Gel content, swell ratio, contact angle measurements,DSC and TGA analysis were performed on films prepared on stainless steelsubstrates. The typical thickness of these films was 0.4 mm. Gelextraction analysis: 91.4% gel, 175% swelling. Contact angle: The waterdroplet spread on the film surface and detached from the needle in about5 minutes. The contact angle of the detached droplet is about 74°±1(n=4). DSC: 1^(st) heat: negative heat flow at 23.5° C. This representsa shift in the T_(g) of pure PTMO polymers (˜−70° C.) towards that ofpure MAA polymers (T_(g) of ˜228° C.). TGA: 2 onset points: (A) 234.9°C., 30.2% mass loss, (B) 407.4° C., 65.5% mass loss. IR: The C═C groupconversion was monitored by FTIR and performed on films prepared on KBrdiscs.

EXAMPLE 28 Hetero Cross-Linked Films of Blended Compound 2 and MethylMethacrylate, Prepared by UV Cure

Compound 2 (3.0335 g), MMA (3.0182 g) and HMP (0.0200 g) were weighed into a 20 mL vial. The vial was vortexed until Compound 2 was completelydissolved. If air bubbles appeared, the vial was allowed to sit at roomtemperature until all bubbles dissipated, before the mixture was castonto the desired substrates (Teflon molds, stainless steel substrates,an aluminum weighing pan and a KBr disc). The Teflon molds, stainlesssteel substrates, weighing pans and KBr disc containing liquid sampleswere placed in the center of the UV box. The box was purged with anargon gas for 1 minute before the UV lamp was turned on for 5 minutes.All substrates were removed from the box and cooled to room temperaturebefore carrying out film analysis. Gel content, swell ratio, contactangle measurements and TGA analysis were performed on films prepared onthe stainless steel substrates. The typical thickness of these films was0.4 mm. XPS analysis was performed on films cast on aluminum weighingpans (0.03 mm thick). Gel extraction analysis: 93.5% gel, 230% swelling.Contact angle: 132.9°±2.2. TGA: 2 onset points: (A) 296.5° C., 27.4%mass loss, (B) 411.4° C., 69.5% mass loss. IR: the C═C group conversionwas monitored by FTIR and performed on films prepared on the KBr discs.Tensile testing: stress at yield=9.2 MPa, stress at break=13.6 MPa,strain at break=9.9%. XPS analysis (90°): C: 47.5%, N:3.93%, O: 11.02%,F: 37.45%.

EXAMPLE 28′ Hetero Cross-Linked Films of Blended Compound 2 and TEGMA,Prepared by UV Cure

Compound 2 (0.37500 g), TEGDMA (0.1250 g) and HMP (0.005 g) were weighedin to a 20 mL vial. The vial was vortexed until Compound 2 wascompletely dissolved. If air bubbles appeared, the vial was allowed tosit at room temperature until all bubbles dissipated, before the mixturewas cast onto the desired substrates (stainless steel substrates, analuminum weighing pan and a KBr disc). The stainless steel substrates,weighing pans and KBr disc containing liquid samples were placed in thecenter of the UV box. The box was purged with an argon gas for 1 minutebefore the UV lamp was turned on for 5 minutes. All substrates wereremoved from the box and cooled to room temperature before carrying outfilm analysis. Gel content, swell ratio, contact angle measurements andTGA analysis were performed on films prepared on stainless steelsubstrates. The typical thickness of these films is 0.4 mm. XPS analysiswas performed on films cast on aluminum weighing pans (0.03 mm thick).Gel extraction analysis: 89.8% gel, 140% swelling. Contact angle: spreadquickly. TGA: 246.5° C., 97.35% mass loss. IR: the C═C group conversionwas monitored by FTIR performed on films cast on KBr disks. XPS analysis(90°): C:49.07%, N: 3.14%, O: 12.56%, F: 35.22%.

EXAMPLE 29 Hetero Cross-Linked Films of Compound 2 and SIBS Polymer,Prepared by UV Cure

SIBS solution (0.5 g/mL in toluene) was cast on stainless steelsubstrates and an aluminum weighing pan. The toluene was allowed toevaporate at room temperature overnight. In a 20 mL vial, Compound 2,HMP, and MeOH (HPLC grade) were weighed. The vial was vortexed until thecomponents were completely well blended. If air bubbles appeared, thevial was allowed to sit at room temperature until all bubbles dissipatedThe Compound 2 solution was transferred from the vial to a 50 mL HDPEspraying bottle. The spraying bottle was used to deposit a thin layer ofCompound 2 and HMP on top of the SIBS film. MeOH solvent was allowed toevaporate at room temperature for 1 hour under an aluminum foil. Thestainless steel substrates and weighing pans containing SIBS filmscoated with Compound 2 and HMP were placed in the center of the UV box.The box was purged with an argon gas for 5 minutes before the UV lampwas turned on for 5 minutes. All substrates were removed from the boxand cooled to room temperature before carrying out film analysis.Contact angle: 128°. XPS analysis (90°): (SIBS) C: 98.90%, N: 0.18%, O:0.45%, F: 0.47%. (SIBS+Compound 2) C: 53.50%, N:3.95%, O:15.11%, F:27.63%.

EXAMPLE 30 Hetero Cross-Linked Films of Compound 2 and EVA Polymer,Prepared by UV Cure

EVA solution (0.5 g/mL in toluene) was cast on stainless steelsubstrates and an aluminum weighing pan. The toluene was allowed toevaporate at room temperature overnight. In a 20 mL vial, Compound 2,HMP, and MeOH (HPLC grade) were weighed. The vial was vortexed until thecomponents were completely well blended. If air bubbles appeared, thevial is allowed to sit at room temperature until all bubbles dissipated.The Compound 2 solution was transferred from the vial to a 50 mL HDPEspraying bottle. The spraying bottle was used to deposit a thin layer ofCompound 2 and HMP on top of the EVA film. MeOH solvent was allowed toevaporate at room temperature for 1 hour under an aluminum foil. Thestainless steel substrates and weighing pans containing EVA films coatedwith Compound 2 and HMP were placed in the center of the UV box. The boxwas purged with an argon gas for 5 minutes before the UV lamp was turnedon for 5 minutes. All substrates were removed from the box and cooled toroom temperature before carrying out film analysis. Contact angle: 126°.XPS analysis (90°): (EVA) C: 84.61%, N: 4.03%, O: 11.36%, F: 0%.(EVA+Compound 2) C: 72.72%, N:4.08%, O: 12.59%, F: 10.21%.

EXAMPLE 31 Hetero Cross-Linked Films Prepared with a Mixture of Compound2 and Compound 6

Compound 2 (0.3 g) was dissolved in toluene (0.1 g/mL) containing BPO (3mg, 1 wt % of Compound 2 mass). Compound 6 (0.3g) was dissolved intoluene (0.1 g/mL) containing BPO (3 mg, 1 wt % of Compound 6 mass).These two solutions were mixed in a 50:50 ratio, and 6 mL of thiscombined solution were cast into 4 cm×4 cm PTFE wells. The PTFE castingplate was placed in a semi-enclosed chamber at room temperature for 1day. The film was then cured for 12 hours in an N₂ purged 60° C. oven.The resulting film was clear, elastomeric, and non-tacky (FIG. 7). Gelextraction analysis (acetone): 96% gel, 141% swelling. Contact angleanalysis: advancing angle: 116°. XPS analysis (90°): (top surface: C:51.4%, N: 2.5%, O: 14.8%, F: 31.1%.) (bottom surface: C: 48.7%, N: 1.9%,O: 13.0%, F: 35.5%).

EXAMPLE 32 Hetero Cross-Linked Films Prepared with a Combination ofCompound 6 and Compound 8

Compound 6 (0.3 g) was dissolved in toluene (0.1 g/mL) containing BPO (3mg, 1 wt % of Compound 6 mass). Compound 8 (0.3g) was dissolved intoluene (0.1 g/mL) containing BPO (3 mg, 1 wt % of Compound 8 mass).These two solutions were mixed in a 50:50 ratio, and 6 mL of thiscombined solution were cast into 4 cm×4 cm PTFE wells. The PTFE castingplate was placed in a semi-enclosed chamber at room temperature for 1day. The film was then cured for 12 hours in an N₂ purged 60° C. oven.The resulting film was clear, elastomeric, resistant to tearing, andnon-tacky (FIG. 8). Gel extraction analysis (acetone): 96% gel, 154%swelling. Contact angle analysis: advancing angle: 127°. XPS analysis(90°): (top surface: C: 54.2%, N: 2.5%, O: 16.4%, F: 26.8%.) (bottomsurface: C: 49.2%, N: 1.8%, O: 12.2%, F: 36.1%).

EXAMPLE 33 Hetero Cross-Linked Films Prepared with a Combination ofCompound 6 and a Vinyl Monomer (FEO1)

Compound 6 (0.3 g) was dissolved in toluene (0.1 g/mL) containing BPO (3mg, 1 wt % of Compound 6 mass). FEO1 (0.3 g) was dissolved in toluene(0.1 g/mL) containing BPO (3 mg, 1 wt % of FEO1 mass). These twosolutions were mixed in a 50:50 ratio, and 6 mL of this combinedsolution were cast into 4 cm×4 cm PTFE wells. The PTFE casting plate wasplaced in a semi-enclosed chamber at room temperature for 1 day. Thefilm was then cured for 12 hours in an N₂ purged 60° C. oven. Theresulting film was clear, elastomeric, resistant to tearing, andnon-tacky (FIG. 9). Gel extraction analysis (acetone): 93% gel, 133%swelling. Contact angle analysis: advancing angle: 104°. XPS analysis(90°): (top surface: C: 47.8%, N: 1.0%, O: 13.4%, F: 36.2%.) (bottomsurface: C: 46.2%, N: 0.6%, O: 11.7%, F: 39.0%).

EXAMPLE 34 Hetero Cross-Linked Films Prepared with a Combination ofCompound 6 and a Vinyl Monomer (HEMA)

Compound 6 (0.3 g) was dissolved in toluene (0.1 g/mL) containing BPO (3mg, 1 wt % of Compound 6 mass). HEMA (0.3g) was dissolved in toluene(0.1 g/mL) containing BPO (3 mg, 1 wt % of HEMA mass). These twosolutions were mixed in a 50:50 ratio, and 6 mL of this combinedsolution were cast into 4 cm×4 cm PTFE wells. The PTFE casting plate wasplaced in a semi-enclosed chamber at room temperature for 1 day. Thefilm was then cured for 12 hours in an N₂ purged 60° C. oven. Theresulting cured material was tough and opaque (FIG. 10). Gel extractionanalysis (acetone): 93% gel, 153% swelling. XPS analysis (90°): (topsurface: C: 53.4%, N: 2.5%, O: 16.2%, F: 27.2%.) (bottom surface: C:51.1%, N: 1.8%, O: 13.1%, F: 33.8%).

EXAMPLE 35 Hetero Cross-Linked Films Prepared with a Combination ofCompound 2 and Compound 1

Compound 2 (0.1 g) was dissolved in toluene (0.1 g/mL) containing BPO (1mg, 1 wt % of Compound 2 mass). Compound 1-ester (0.1 g) was dissolvedin toluene (0.1 g/mL) containing BPO (1 mg, 1 wt % of Compound 1-estermass). These two solutions were mixed in a 50:50 ratio, and 2 mL of thiscombined solution were cast into 2 cm×2 cm PTFE wells. The PTFE castingplate was placed in a semi-enclosed chamber at room temperature for 1day. The film was then cured for 12 hours in an N₂ purged 60° C. oven.The resulting cured material was homogeneous and firm. Gel extractionanalysis (acetone): 87% gel. XPS analysis (90°): top surface: C: 41.4%,N: 1.1%, O: 9.9%, F: 45.4%.

EXAMPLE 36 Homo Cross-Linked Films Prepared Using HEMA Monomer

HEMA (0.6 g) was dissolved in toluene (6 mL, 0.1 g/mL) containing BPO (6mg, 1 wt % of HEMA mass), and this solution was cast into a 4 cm×4 cmPTFE well. The PTFE casting plate was placed in a semi-enclosed chamberat room temperature for 1 day. The film was then cured for 12 hours inan N₂ purged 60° C. oven. The resulting cured material was hard andinconsistent in thickness. Gel extraction analysis (acetone): >99% gel,136% swelling.

EXAMPLE 37 Homo Cross-Linked Films Prepared Using FEO1 Monomer

FEO1 (0.6 g) was dissolved in toluene (6 mL, 0.1 g/mL) containing BPO (6mg, 1 wt % of FEO1 mass), and this solution was cast into a 4 cm×4 cmPTFE well. The PTFE casting plate was placed in a semi-enclosed chamberat room temperature for 1 day. The film was then cured for 12 hours inan N₂ purged 60° C. oven. The resulting cured material was hard andinconsistent in thickness. Gel extraction analysis (acetone): 84% gel.

EXAMPLE 38 Hetero Cross-Linked Films Prepared Using a Blend of Compound1 and HEMA Monomer

Compound 1-ester (0.3 g) was dissolved in toluene (0.1 g/mL) containingBPO (3 mg, 1 wt % of Compound 1-ester mass). HEMA (0.3g) was dissolvedin toluene (0.1 g/mL) containing BPO (3 mg, 1 wt % of HEMA mass). Thesetwo solutions were mixed in a 50:50 ratio, and 6 mL of this combinedsolution were cast into 4 cm×4 cm PTFE wells. The PTFE casting plate wasplaced in a semi-enclosed chamber at room temperature for 1 day. Thefilm was cured for 12 hours in an N₂ purged 60° C. oven. The resultingcured material was more firm than pure Compound 1 but shrank within thecasting form, and was too soft to handle as a film.

EXAMPLE 39 Hetero Cross-Linked Films Prepared Using a Blend of Compound1 and FEO1 Monomer

Compound 1-ester (0.3 g) was dissolved in toluene (0.1 g/mL) containingBPO (3 mg, 1 wt % of Compound 1-ester mass). FEO1 (0.3g) was dissolvedin toluene (0.1 g/mL) containing BPO (3 mg, 1 wt % of FEO1 mass). Thesetwo solutions were mixed in a 50:50 ratio, and 6 mL of this combinedsolution were cast into 4 cm×4 cm PTFE wells. The PTFE casting plate wasplaced in a semi-enclosed chamber at room temperature for 1 day. Thefilm was then cured for 12 hours in an N₂ purged 60° C. oven. Theresulting cured material was firm and even-looking within the castingform, but was too soft to handle as a film.

Polymerization on a Stent Platform EXAMPLE 40 Coating of Compound 2 on aStent, Prepared by Spraying and Heat Cure

Compound 2 (200 mg) was dissolved in toluene (4 mL, 0.05 g/mL), stirredfor 90 minutes at room temperature and BPO (2 mg, 1 wt % of Compound 2mass) was added and the mixture was stirred for an additional 30minutes. The solution blend was sprayed onto stents using an EFD spraysystem, and the coatings were cured at 60° C. in an N₂ purged oven for12 hours. SEM analysis (FIG. 11) indicated that the stents wereuniformly coated. In addition, a Compound 2 coated stent was crimped ona balloon and deployed at 10 psi. Coating remained intact (FIG. 12).

EXAMPLE 41 Coating of Compound 6 on a Stent, Prepared by Spraying andHeat Cure

Compound 6 (200 mg) was dissolved in toluene (4 mL, 0.05 g/mL), stirredfor 90 minutes at room temperature and BPO (2 mg, 1 wt % of Compound 6mass) was added and the mixture was stirred for an additional 30minutes. The solution blend was sprayed onto stents using an EFD spraysystem, and the coatings were cured at 60° C. in an N₂ purged oven for12 hours. SEM analysis (FIG. 13) indicated that the stents wereuniformly coated. A Compound 6 coated stent was extracted with tolueneafter curing for 24 hrs and SEM images suggested that the coatingremained intact after solvent extraction (FIG. 14). In addition,Compound 6 coated stent was also extracted in PBS 7.4 buffer for 24 hrsand SEM images suggested that the coating remained intact after bufferextraction (FIG. 15).

EXAMPLE 42 Coating of Compound 8 on a Stent, Prepared by Spraying andHeat Cure

Compound 8 (200mg) was dissolved in toluene (4 mL, 0.05 g/mL), stirredfor 90 minutes at room temperature and BPO (2 mg, 1 wt % of Compound 8mass) was added and the mixture was stirred for an additional 30minutes. The solution blend was sprayed onto stents using an EFD spraysystem, and the coatings were cured at 60° C. in an N₂ purged oven for12 hours. SEM analysis (FIG. 16) indicated that the stents wereuniformly coated.

EXAMPLE 43 Coating of Compound 12 on a Stent, Prepared by Spraying andHeat Cure (Toluene Solvent)

Compound 12 (200 mg) was dissolved in toluene (4 mL, 0.05 g/mL), stirredfor 90 minutes at room temperature and BPO (2 mg, 1 wt % of Compound 12mass) was added and the mixture was stirred for an additional 30minutes. The solution blend was sprayed onto stents using an EFD spraysystem, and the coatings were cured at 60° C. in an N₂ purged oven for12 hours. SEM analysis (FIG. 17) indicated that the stents showed decentcoating.

EXAMPLE 44 Coating of Compound 12 on a Stent, Prepared by Spraying andHeat Cure (Toluene/THF Solvent)

Compound 12 (200 mg) was dissolved in 75:25 toluene:THF (4 mL, 0.05g/mL), stirred for 90 minutes at room temperature and BPO (2 mg, 1 wt %of Compound 12 mass) was added and the mixture was stirred for anadditional 30 minutes. The solution blend was sprayed onto stents usingan EFD spray system, and the coatings were cured at 60° C. in an N₂purged oven for 12 hours. SEM analysis (FIG. 18) indicated that thestents were uniformly coated.

EXAMPLE 45 Coating of a Mixture of Compound 2 and Compound 6 on a Stent,Prepared by Spraying and Heat Cure

Compound 2 and Compound 6 (1:1, total 200 mg) were dissolved in toluene(4 mL, 0.05 g/mL), stirred for 90 minutes at room temperature and BPO (2mg, 1 wt % of Compound 2 and Compound 6 combined mass) was added and themixture was stirred for an additional 30 minutes. The solution blend wassprayed onto stents using an EFD spray system, and the coatings werecured at 60° C. in an N₂ purged oven for 12 hours. SEM analysis (FIG.19) indicated that the stents were uniformly coated.

EXAMPLE 46 Coating of a Mixture of Compound 6 and Compound 8 on a Stent,Prepared by Spraying and Heat Cure

Compound 6 and Compound 8 (1:1, total 200 mg) were dissolved in toluene(4 mL, 0.05 g/mL), stirred for 90 minutes at room temperature and BPO (2mg, 1 wt % of Compound 6 and Compound 8 combined mass) was added and themixture was stirred for an additional 30 minutes. The solution blend wassprayed onto stents using an EFF spray system, and the coatings werecured at 60° C. in an N₂ purged oven for 12 hours. SEM analysis (FIG.20) indicated that the stents were uniformly coated.

EXAMPLE 47 Coating of a Mixture of Compound 6 and Paclitaxel on a Stent,Prepared by Spraying and Heat Cure

Compound 6 (200 mg) was dissolved in 75:25 toluene:THF (4 mL, 0.05g/mL), stirred for 90 minutes at room temperature and Paclitaxel (17.6mg, 8.8wt % of Compound 6 mass) and BPO (2 mg, 1 wt % of Compound 6mass) was added and the mixture was stirred for an additional 30minutes. The solution blend was sprayed onto stents using an EFD spraysystem, and the coatings were cured at 60° C. in an N₂ purged oven for12 hours. SEM analysis (FIG. 21) indicated that the stents wereuniformly coated.

Biocompatibility Assays EXAMPLE 48 MEM Elution Assay of Compound 2

Samples of film from Example 19 (1 cm×2 cm) were weighed and incubatedin MEM media for 24 hours. A counted aliquot of L-929 mouse fibroblastculture was seeded into each MEM extract, and stability of the cellpopulation was evaluated after 24 hours using a trypan blue exclusionmethod. By this cytotoxicity evaluation method, the Compound 2 filmswere non-toxic.

EXAMPLE 49 Homo Cross-Linked Films of Compound 2 Prepared by Heat Cure,Assessed for Inflammatory Cell Interaction

Compound 2 was dissolved in toluene (0.1 g/mL) containing BPO initiator(1 wt % of Compound 2 mass). The toluene solution was cast into 96 wellpolypropylene plates (6 wells per plate), and the plates were placed ina semi-enclosed chamber at room temperature for 1 day. The Compound 2films were then cured for 12 hours in an N₂ purged 60° C. oven, andvacuum dried. For comparison purposes, films of SIBS were cast in asecond 96 well plate: a 0.1 g/mL toluene solution of SIBS was cast in 6wells, the plates were placed in a semi-enclosed chamber at roomtemperature for 1 day, dried in a 60° C. oven for 1 day, and vacuumdried. Into the plate containing SIBS were inserted 316 stainless steelinserts. The plates were sterilized under a UV lamp for 1 hour, afterwhich each sample well was hydrated using 200 uL PBS. Approximately2.5×10⁵ U937 monocyte-like cells were seeded onto each sample in thepresence of PMA, and were incubated at 37° C. in a humid incubator forthree days. The adherent U937 macrophages were enumerated using aCyQuant assay (FIG. 27). In a similar experiment, the Compound 2 andSIBS films were prepared on stainless steel inserts (FIG. 28).

EXAMPLE 50 Cone-and-Plate Assay of Homo Cross-Linked Films of Compound 2

Samples of Compound 2 film from Example 19 and 316 stainless steel (4cm×4 cm) were fixed into individual wells of a cone-and-plate device. A1.2 mL aliquot of whole blood suspension containing ⁵¹Cr labeledplatelets (250 000 platelets/μL) and ¹²⁵I labeled fibrinogen waspipetted onto the films, and cones were lowered into each well andimmediately rotated at 200 rpm for 15 minutes. The films were thenremoved, rinsed, and adherent platelets and fibrinogen quantified by agamma counter (FIG. 29).

EXAMPLE 51 MEM Elution Assay of Homo Cross-Linked Films of Compound 6

Samples of film from Example 20 (1 cm×2 cm) were weighed and incubatedin MEM media for 24 hours. A counted aliquot of L-929 mouse fibroblastculture was seeded into each MEM extract, and stability of the cellpopulation was evaluated after 24 hours using a trypan blue exclusionmethod. By this cytotoxicity evaluation method, the Compound 6 filmswere non-toxic.

EXAMPLE 52 Homo Cross-Linked Films of Compound 6 Prepared by Heat Cure,Assessed for Inflammatory Cell Interaction

Compound 6 was dissolved in toluene (0.1 g/mL) containing BPO initiator(1 wt % of Compound 6 mass). The toluene solution was cast into 96 wellpolypropylene plates (6 wells per plate), and the plates were placed ina semi-enclosed chamber at room temperature for 1 day. The Compound 6films were then cured for 12 hours in an N₂ purged 60° C. oven, andvacuum dried. For comparison purposes, films of SIBS were cast in asecond 96 well plate: a 0.1 g/mL toluene solution of SIBS was cast in 6wells, the plates were placed in a semi-enclosed chamber at roomtemperature for 1 day, dried in a 60° C. oven for 1 day, and vacuumdried. Into the plate containing SIBS were also inserted 316 stainlesssteel inserts. The plates were sterilized under a UV lamp for 1 hour,after which each sample well was hydrated using 200 uL PBS.Approximately 2.5×10⁵ U937 monocyte-like cells were seeded onto eachsample in the presence of PMA, and were incubated at 37° C. in a humidincubator for three days. The adherent U937 macrophages were enumeratedusing a CyQuant assay (FIG. 27). In a similar experiment, the Compound 6and SIBS films were prepared on stainless steel inserts (FIG. 28).

EXAMPLE 53 Cone-and-Plate Assay of Homo Cross-Linked Films of Compound 6

Samples of Compound 6 film from Example 20 and 316 stainless steel (4cm×4 cm) were fixed into individual wells of a cone-and-plate device. A1.2 mL aliquot of whole blood suspension containing ⁵¹Cr labeledplatelets (250 000 platelets/μL) and ¹²⁵I labeled fibrinogen waspipetted onto the films, and cones were lowered into each well andimmediately rotated at 200 rpm for 15 minutes. The films were thenremoved, rinsed, and adherent platelets and fibrinogen quantified by agamma counter (FIG. 29).

EXAMPLE 54 Homo Cross-Linked Films of Compound 8 Prepared by Heat Cure,Assessed for Inflammatory Cell Interaction

Compound 8 was dissolved in toluene (0.1 g/mL) containing BPO initiator(1 wt % of Compound 8 mass). The toluene solution was cast into 96 wellpolypropylene plates (6 wells per plate), and the plates were placed ina semi-enclosed chamber at room temperature for 1 day. The Compound 8films were then cured for 12 hours in an N₂ purged 60° C. oven, andvacuum dried. For comparison purposes, films of SIBS were cast in asecond 96 well plate: a 0.1 g/mL toluene solution of SIBS was cast in 6wells, the plates were placed in a semi-enclosed chamber at roomtemperature for 1 day, dried in a 60° C. oven for 1 day, and vacuumdried. Into the plate containing SIBS were also inserted 316 stainlesssteel inserts. The plates were sterilized under a UV lamp for 1 hour,after which each sample well was hydrated using 200 uL PBS.Approximately 2.5×10⁵ U937 monocyte-like cells were seeded onto eachsample in the presence of PMA, and were incubated at 37° C. in a humidincubator for three days. The adherent U937 macrophages were enumeratedusing a CyQuant assay (FIG. 27). In a similar experiment, the Compound 8and SIBS films were prepared on stainless steel inserts (FIG. 28).

EXAMPLE 55 Homo Cross-Linked Films of Compound 12 Prepared by Heat Cure,Assessed for Inflammatory Cell Interaction

Compound 12 was dissolved in toluene (0.1 g/mL) containing BPO initiator(1 wt % of Compound 12 mass). The toluene solution was cast into 96 wellpolypropylene plates (6 wells), and the plates were placed in asemi-enclosed chamber at room temperature for 1 day. The Compound 12films were then cured for 12 hours in an N₂ purged 60° C. oven, andvacuum dried. For comparison purposes, films of SIBS were cast in asecond 96 well plate: a 0.1 g/mL toluene solution of SIBS was cast in 6wells, the plates were placed in a semi-enclosed chamber at roomtemperature for 1 day, dried in a 60° C. oven for 1 day, and vacuumdried. Into the plate containing SIBS were also inserted 316 stainlesssteel inserts. The plates were sterilized under a UV lamp for 1 hour,after which each sample well was hydrated using 200 uL PBS.Approximately 2.5×10⁵ U937 monocyte-like cells were seeded onto eachsample in the presence of PMA, and were incubated at 37° C. in a humidincubator for three days. The adherent U937 macrophages were enumeratedusing a CyQuant assay (FIG. 27). In a similar experiment, the Compound12 and SIBS films were prepared on stainless steel inserts (FIG. 28).

Drug Inclusion and Release

Compounds from Section 1 provide a polymeric platform with functionalgroups suitable for the immobilization and inclusion of active agents.Compounds 6, 7, and 8 have functional groups for covalent interactionwith active agents. Films or stent coatings including active agents areprepared according to Section 2 and 3 methods.

EXAMPLE 56 Films of Compound 2 and Aspirin (90:10), UV Cure

Compound 2 (1.6481 g), ASA (0.1841 g), HMP (0.0088 g) and MeOH (HPLCgrade, 4.01 g) were weighed in to a 20 mL vial. The vial was vortexeduntil all components were well mixed. If air bubbles appeared, the vialwas allowed to sit at room temperature until all bubbles dissipated,before the mixture was cast onto desired substrates (stainless steeldiscs, an aluminum weighing pan and a KBr disc). The MeOH was evaporatedoff at room temperature for 1 and 24 hours under aluminum foil. After 1hour, the stainless steel substrates, aluminum weighing pan and KBr disccontaining liquid samples were placed in the center of the UV box. Thebox was purged with an argon gas for 10 minutes before the UV lamp wasturned on for 2 minutes. All substrates were removed from the box andcooled to room temperature before carrying out film analysis. After 24hours, the UV cure procedure was repeated for samples cast on Teflonsubstrates. Gel content, swell ratio, contact angle measurements, DSCand TGA analysis were performed on films prepared on stainless steelsubstrates. The typical thickness of these films was 0.4 mm. XPSanalysis was performed on films cast on aluminum weighing pans (0.03 mmthick). Gel content: 82%, swelling=180%. Contact angle: 131.8°±2.0. DSC:negative heat flow at −64° C. (associated with the T_(g) of PTMO). TGA:2 onset points: (A) 234.9° C., 30.2% mass loss, (B) 407.4° C., 65.5%mass loss. IR: the C═C group conversion is monitored by FTIR andperformed on films prepared on KBr discs. XPS: C: 50.68%, N: 3.02%, O:12.00%, F: 34.31%. Aspirin release was examined for films cast in Teflonmolds (FIG. 22).

EXAMPLE 57 Films of Compound 2 and Aspirin (75:25), UV Cure

Compound 2 (100 mg), HMP (1 mg) and ASA (33 mg) were dissolved in DMSOas a 2.5 g/mL solution. The solution was cast into a 4 mL glass vial andthe material was cured under UV light for 2 minutes. The resulting clearelastomeric film was incubated in PBS solutions for 24 hours at 37° C.,with measurement of ASA release made at 1, 2, 3, 4, 7 and 24 hours by UVspectrophotometer measurement (FIG. 23).

EXAMPLE 58 Films of Compound 2 and Ibuprofen (75:25), Heat Cure

Ibuprofen was mixed with Compound 2 (25 wt % of total mass) in toluene(0.1 gram/mL) containing BPO (1 wt %), and cured at 60° C. under N₂. Therelease of ibuprofen from the cured film was measured over 96 hours inPBS solution at 37° C. by UV spectrophotometer measurement (FIG. 24).

EXAMPLE 59 Films of Compound 2 and Ciprofloxacin-HEMA (Compound 17)

N-trityl ciprofloxacin, EDC, and DMAP (in a stoichiometory of 1:8:0.5molar ratio) were dissolved in anhydrous DCM. 10% excess HEMA relativeto the mole of COOH groups was then added into the reaction system. Thereaction mixture was stirred at room temperature under N₂ for 7 days.After rotary evaporated the solvent, the solid residual was extracted bydiethyl ether at room temperature. The crude product of this reactionwas roughly dried and then was dissolved in DCM. TFAc (10 vol % of DCM)was added in the solution, stirred at room temperature for 14 hours. Thesolvent was removed by rotary evaporation at room temperature. The solidcrude product was stirred in diethyl ether and filtered three times. Theprecipitated product (Compound 17) was dried under vacuum at roomtemperature. ¹⁹F NMR (300 MHz, DMSO): found one multiple peak at −120.8ppm. ¹H NMR (300 MHz, CDCl₃) found: δ (ppm): 8.44 (s, FC_(cip)CH), 7.80(b, FC_(cip)CCH), 7.5 (b, OC_(cip)CHN), 6.10 (s, HCH═C_(HEMA)), 5.70 (s,HCH═C_(HEMA)), 4.40 (s, OCH₂CH₂O_(HEMA)), 3.45 (br, N_(cip)CHCH ₂CH ₂),2.80 (s, _(HEMA)CCH₃), 1.77 (s, _(cip)NCH ₂CH₂N), 1.25 (m,_(cip)NCH₂CH₂NH), 1.25 (m, _(cip)NCH₂CH₂NH), 1.12 (t, _(cip)NH).

Compound 17 (0.050 g), Compound 2 (0.500 g), BPO (0.0055 g) and pyridine(2 ml) were transferred to a 20 mL vial. The vial was vortexed until thecomponents were completely well blended. The mixture was cast onto thedesired substrates including stainless steel discs and an aluminumweighing pan. Pyridine solvent was allowed to evaporate at roomtemperature for 17 hours under an aluminum foil in a fume hood. Thestainless steel substrates and aluminum weighing pan containing liquidsamples were placed in an oven. The oven was purged with N₂ for threetimes before the heat was turned on to 110° C. for 17 hours. During thistime, a gentle stream of N₂ was kept on positive flow through the oven.After 17 hours curing at 110° C., samples were cooled to roomtemperature under N₂, and removed from the oven for analysis. Gelcontent, swell ratio, contact angle measurements, DSC and TGA analyseswere performed on films prepared on stainless steel substrates. XPSanalysis was performed on films cast on aluminum weighing pans (0.03 mmthick). Gel extraction (acetone): 86.2% gel, 220% swelling. Contactangle: 109°. XPS analysis (90°): C:54.77%, N: 4.15%, O: 15.14%, F:24.85%. DSC: negative heat flow at −69° C. (associated with the T_(g) ofthe PTMO). TGA: 2 onset points: (A) 227° C., 19% mass loss, (B) 392° C.,76% mass loss.

EXAMPLE 60 Films of Compound 2 and Hydrocortisone-MA (Compound 18)

Hydrocortisone (2.5 g, 6.90 mmol) was transferred to a flame-dried 250mL reaction flask equipped with a stir bar. The flask was capped by arubber septum and filled with N₂ provided by a balloon. Anhydrous DCM(100 mL) was transferred to the flask via a syringe. Hydrocortisone didnot dissolve in DCM completely, forming a milky suspension. TEA (1.10ml, 7.89 mmol) was transferred to the reaction flask by a syringe. Asolution of acryloyl chloride (0.65 g, 7.18 mmol in 10 ml of dry DCM)was added dropwise to the reaction flask via a syringe. The additiontook about 10 minutes. As the solution of acryloyl chloride was added,the suspension became less milky. The reaction flask was kept stirringfor 16 hours at room temperature. About 80 mL of DCM was removed byrotary evaporator to give a milky suspension. Flash columnchromatography of the milky suspension using DCM as the eluent yieldedpure hydrocortisone-containing acrylate, Compound 18. R_(f) of Compound18 in diethyl ether containing 2 wt % ethanol as the inhibitor: 0.46. ¹HNMR (300 MHz, CDCl₃) found: δ (ppm) 6.49 (1H, dd, —OCCHCH₂), 6.23 (1H,dd, —OCHCH ₂), 5.92 (1H, dd, —CHCH ₂), 5.68 (1H, s, C⁴ _(HC) H), 5.13(1H, d, OCCH ₂O—), 4.94 (1H, d, OCCH ₂O—), 4.48 (1H, b, C¹¹ _(HC)HOH),2.87 (1H, m, C¹¹ _(HC) HOH), 2.60-0.94 (25H, m, C¹ _(HC) H ₂, C² _(HC) H₂, C⁶ _(HC) H ₂, C⁷ _(HC) H ₂, C⁸ _(HC) H, C⁹ _(HC) H, C¹² _(HC) H ₂,C¹⁴ _(H) H, C¹⁵ _(HC) H ₂, C¹⁶ _(HC) H ₂, C¹⁸ _(HC) H ₃, C¹⁹ _(HC) H ₃.

Compound 18 (0.050 g), Compound 2 (0.500 g), BPO (0.0055 g) and pyridine(2 ml) were transferred to a 20 mL vial. The vial was vortexed until thecomponents were completely well blended. The mixture was cast onto thedesired substrates including stainless steel discs and an aluminumweighing pan. Pyridine solvent was allowed to evaporate at roomtemperature for 17 hours under an aluminum foil in a fume hood. Thestainless steel substrates and aluminum weighing pan containing liquidsamples were placed in an oven. The oven was purged with N₂ for threetimes before the heat was turned on to 110° C. for 17 hours. During thistime, a gentle stream of N₂ was kept on positive flow through the oven.After 17 hours curing at 110° C., samples were cooled to roomtemperature under an N₂ environment, and removed from the oven foranalysis. Gel content, swell ratio, contact angle measurements, DSC andTGA analyses were performed on films prepared on stainless steelsubstrates. XPS analysis was performed on films cast on aluminumweighing pans (0.03 mm thick). Gel extraction (acetone): 96.8% gel, 161%swelling. Contact angle: 109°. XPS analysis (90°): C:50.94%, N: 3.38%,O: 11.41%, F: 34.27%. DSC: negative heat flow at −68.7° C. (associatedwith the T_(g) of the PTMO). TGA: 2 onset points: (A) 251° C., 17% massloss, (B) 409° C., 78% mass loss.

EXAMPLE 61 Films of Compound 6 and Hydrocortisone (99:1), Heat Cure

Hydrocortisone was mixed with Compound 6 (1 wt % of total mass) intoluene (0.1 gram/mL) containing initiator (1 wt %), and cured at 60° C.under N₂. The release of hydrocortisone from the cured film was measuredover 24 hours in PBS solution at 37° C. by HPLC measurement (FIG. 25). Astent was coated using the same casting solution and cure method (FIG.26).

EXAMPLE 62 Films of Compound 6 and Dexamethasone (99:1), Heat Cure

Dexamethasone was mixed with Compound 6 (1 wt % of total mass) intoluene (0.1 gram/mL) containing initiator (1 wt %), and cured at 60° C.under N₂. The release of dexamethasone from the cured film was measuredover 24 hours in PBS solution at 37° C. by HPLC measurement (FIG. 25).

Other Embodiments

All publications, patents, and patent applications mentioned in thisspecification are herein incorporated by reference to the same extent asif each independent publication or patent application was specificallyand individually indicated to be incorporated by reference.

While the invention has been described in connection with specificembodiments thereof, it will be understood that it is capable of furthermodifications and this application is intended to cover any variations,uses, or adaptations of the invention following, in general, theprinciples of the invention and including such departures from thepresent disclosure that come within known or customary practice withinthe art to which the invention pertains and may be applied to theessential features hereinbefore set forth, and follows in the scope ofthe claims.

Other embodiments are within the claims.

1. A monomer comprising: i. two or more cross-linking domains, and ii.an oligomeric segment having a first end covalently tethered to a firstcross-linking domain and a second end covalently tethered to a secondcross-linking domain, wherein at least one of said cross-linking domainsis an oligofluorinated cross-linking domain.
 2. The monomer of claim 1,further described by formula (I):(D)-[(oligo)-(D)]_(n)   (I) wherein oligo is an oligomeric segment; eachD is a cross-linking domain; and n is an integer from 1 to 20, whereinat least one D is an oligofluorinated cross-linking domain.
 3. Themonomer of claim 1, further described by formula (II):(D)-[(oligo)-(LinkA-F_(T))]_(m)-[(oligo)-(D)]_(n)   (II) wherein oligois an oligomeric segment; each D is a cross-linking domain; F_(T) is anoligofluoro group; each LinkA-F_(T) is an organic moiety covalentlybound to a first oligo, a second oligo, and F_(T); n is an integer from1 to 20; and m is an integer from 1 to 20, wherein at least one D is anoligofluorinated cross-linking domain.
 4. The monomer of claim 1,wherein said cross-linking domains include a reactive moiety selectedfrom vinyls, epoxides, aziridines, and oxazolines.
 5. The monomer of anyof claims 1-4, wherein said oligofluorinated cross-linking domain isselected from


6. The monomer of claim 1, further described by formula (III):(oligo)_(n)(vinyl)_(m)(F_(T))_(o)   (III) wherein oligo is an oligomericsegment; vinyl is a cross-linking domain comprising an unsaturatedmoiety capable of undergoing radical initiated polymerization; F_(T) isan oligofluoro group covalently tethered to said vinyl and/or saidoligo; and each of n, m, and o is, independently, an integer from 1 to 5wherein said monomer comprises at least one oligofluorinatedcross-linking domain.
 7. The monomer of claim 6, further described byformula (IV):

wherein oligo is an oligomeric segment; vinyl is a cross-linking domaincomprising an unsaturated moiety capable of undergoing radical initiatedpolymerization; F_(T) is an oligofluoro group; each LinkA is,independently, an organic moiety covalently bound to oligo, F_(T), andvinyl; and a, b, and c are integers greater than
 0. 8. The monomer ofany of claims 3 to 7, wherein F_(T) has the formula:CF₃(CF₂)_(p)X, (CF₃)₂CF(CF₂)_(p)X, or (CF₃)₃C(CF₂)_(p)X, wherein X isselected from CH₂CH₂—, (CH₂CH₂O)_(n), CH₂CH(OD)CH₂O—, CH₂CH(CH₂OD)O—, orD-; D is a moiety capable of chain growth polymerization; p is aninteger between 2 and 20; and n is an integer between 1 and
 10. 9. Themonomer of any of claims 4-8, wherein said vinyl group is selected frommethylacrylate, acrylate, allyl, vinylpyrrolidone, and styrenederivatives.
 10. The monomer of any of claims 4-8, wherein said oligo isselected from polyurethane, polyurea, polyamides, polyaklylene oxide,polycarbonate, polyester, polylactone, polysilicone, polyethersulfone,polypeptide, polysaccharide, polysiloxane, polydimethylsiloxane,polypropylene oxide, polyethylene oxide, polytetramethyleneoxide, andcombinations thereof.
 11. The monomer of any of claims 1-10, furthercomprising one or more biologically active agents covalently tethered tosaid monomer.
 12. The monomer of claim 11, wherein said biologicallyactive agent is selected from proteins, peptides, carbohydrates,antibiotics, antiproliferative agents, rapamycin macrolides, analgesics,anesthetics, antiangiogenic agents, antithrombotic agents, vasoactiveagents, anticoagulants, immunomodulators, cytotoxic agents, antiviralagents, antibodies, neurotransmitters, psychoactive drugs,oligonucleotides, proteins, vitamins, lipids, and prodrugs thereof. 13.A method for coating an article said method comprising the steps of (a)contacting said article with a monomer of any of claims 1-12 and (b)polymerizing said monomer to form a cross-linked coating.
 14. A methodfor making a shaped article said method comprising the steps of (a)polymerizing a monomer of any of claims 1-12 to form a base polymer and(b) shaping said base polymer to form a shaped article.
 15. The methodof claim 13 or 14, wherein said shaped article is an implantable medicaldevice.
 16. The method of claim 15, wherein said implantable medicaldevice is selected from cardiac-assist devices, catheters, stents,prosthetic implants, artificial sphincters, and drug delivery devices.17. The implantable medical device of claim 16, wherein said implantablemedical device is a stent.
 18. The method of claim 13 or 14, whereinsaid shaped article is a nonimplantable medical device.
 19. The methodof any of claims 13-18, wherein said polymerizing is initiated by heat,UV radiation, a photoinitiator, or a free-radical initiator.
 20. Themethod of claim 19, wherein said polymerizing is initiated by heat. 21.The method of any of claims 13-18, wherein said polymerizing furthercomprises mixing said monomer with a second compound containing a vinylgroup.
 22. The method of claim 21, wherein said second compound is amonomer of any of claims 1-12.
 23. The method of claim 22, wherein saidsecond vinyl monomer is selected from acrylic acid, methyl acrylate,ethyl acrylate, n-butyl acrylate, 2-hydroxyethyl acrylate, n-butylacrylate, glycidyl acrylate, vinyl acrylate, allyl acrylate,2-hydroxyethyl acrylate, 2-hydroxy ethyl methacrylate (HEMA), 2-aminoethyl methacrylate, glycerol monomethacrylate, acrylamide,methacrylamide, N-(3-aminopropyl)methacrylamide, crotonamide, allylalcohol, and 1,1,1-trimethylpropane monoallyl ether.
 24. A method forencapsulating a biologically active agent in a polymer, said methodcomprising (a) contacting a biologically active agent with a monomer ofany of claims 1-12 and (b) polymerizing said monomer to form anoligofluorinated cross-linked polymer.
 25. The method of claim 24,wherein said biologically active agent is selected from proteins,peptides, carbohydrates, antibiotics, antiproliferative agents,rapamycin macrolides, analgesics, anesthetics, antiangiogenic agents,antithrombotic agents, vasoactive agents, anticoagulants,immunomodulators, cytotoxic agents, antiviral agents, antibodies,neurotransmitters, psychoactive drugs, oligonucleotides, vitamins,lipids, and prodrugs thereof.
 26. A composition comprising: (i) a firstcomponent having a core substituted with m nucleophilic groups, wherem≧2; and a second component having a core substituted with nelectrophilic groups, where n≧12 and m+n>4; wherein the composistioncomprises at least one oligofluorinated nucleophilic group or oneoligofluorinated electrophilic group, and wherein the first componentand the second component react to form oligofluorinated cross-linkedpolymer.
 27. The composition of claim 26, wherein said first componentcomprises an oligomeric segment having a first end covalently tetheredto a first nucleophilic group and a second end covalently tethered to asecond nucleophilic group, wherein said first nucleophilic group or saidsecond nucleophilic group is an oligofluorinated nucleophilic group. 28.The composition of claim 26, wherein said second component comprises anoligomeric segment having a first end covalently tethered to a firstelectrophilic group and a second end covalently tethered to a secondelectrophilic group, wherein said first electrophilic group or saidsecond electrophilic group is an oligofluorinated nucleophilic group.29. The composition of claim 26, wherein said first component or saidsecond component is further described by formula (V):(G)-[(oligo)-(G)]_(n)   (V) wherein oligo is an oligomeric segment; G iseither a nucleophilic group or an electrophilic group; and n is aninteger from 1 to 5, wherein at least one G is an oligofluorinatednucleophilic group or oligofluorinated electroophilic group.
 30. Thecomposition of claim 26, wherein said first component or said secondcomponent is further described by formula (VI):

wherein oligo is an oligomeric segment; G is either a nucleophilic groupor an electrophilic group; F_(T) is an oligofluoro group; each LinkA is,independently, an organic moiety covalently bound to oligo, F_(T), andG; and a, b, and c are integers greater than
 0. 31. The composition ofclaim 30, wherein F_(T) has the formula:CF₃(CF₂)_(p)X, (CF₃)₂CF(CF₂)_(p)X, or (CF₃)₃C(CF₂)_(p)X, wherein X isselected from CH₂CH₂—, (CH₂CH₂O)_(n), CH₂CH(OD)CH₂O—, CH₂CH(CH₂OD)O—, orD-; D is a moiety capable of chain growth polymerization; p is aninteger between 2 and 20; and n is an integer between 1 and
 10. 32. Thecomposition of any of claims 26 to 31, wherein said nucleophilic groupsand said electrophilic groups undergo a nucleophilic substitutionreaction, a nucleophilic addition reaction, or both.
 33. The compositionof claim 32, wherein the nucleophilic groups are selected from primaryamines, secondary amines, thiols, alcohols, and phenols.
 34. Thecomposition of claim 32, wherein the electrophilic groups are selectedfrom carboxylic acid esters, acid chloride groups, anhydrides,isocyanato, thioisocyanato, epoxides, activated hydroxyl groups,succinimidyl ester, sulfosuccinimidyl ester, maleimido, andethenesulfonyl.
 35. The composition of claim 26, wherein the number ofnucleophilic groups in the mixture is approximately equal to the numberof electrophilic groups in the mixture.
 36. The composition of claim 35,wherein the ratio of moles of nucleophilic groups to moles ofelectrophilic groups is about 2:1 to 1:2.
 37. The composition of claim36, wherein the ratio is 1:1.
 38. A method for coating an article saidmethod comprising the steps of (a) contacting said article with acomposition of any of claims 26-37; and (b) polymerizing saidcomposition on said article to form a cross-linked coating.
 39. A methodfor making a shaped article said method comprising the steps of (a)polymerizing a composition of any of claims 26-37 to form a base polymerand (b) shaping said base polymer to form a shaped article.
 40. Themethod of claim 38 or 39, wherein said article is an implantable medicaldevice.
 41. The method of claim 40, wherein said implantable medicaldevice is selected from cardiac-assist devices, catheters, stents,prosthetic implants, artificial sphincters, and drug delivery devices.42. The method of claim 41, wherein said implantable medical device is astent.
 43. The method of claim 38 or 39, wherein said article is anonimplantable medical device.
 44. A method for coating a stentcomprising initiating a polymerization reaction on the surface of saidstent to form a polymerized coating.
 45. The method of claim 44, whereinsaid polymerized coating is a cross-linked polymer coating.
 46. Themethod of claim 45, wherein said polymerized coating is anoligofluorinated cross-linked polymer coating.
 47. The method of claim44, wherein said polymerization reaction is a chain growthpolymerization reaction.
 48. The method of claim 44, wherein saidpolymerization reaction is a nucleophilic substitution reaction and/or anucleophilic addition reaction.
 49. The method of any of claims 44-48,comprising the steps of (a) contacting said stent with a monomer of anyof claims 1-12 or a composition of any of claims 26-36; and (b)polymerizing said monomer or polymerizing said composition to form across-linked coating.
 50. The method of claim 13 or 38, wherein anuncoated implantable medical device is coated to produce a coatedimplantable medical device, said coated implantable medical devicehaving, upon implantation into an animal, reduced protein deposition,reduced fibrinogene deposition, reduced platelet deposition, or reducedinflammatory cell adhesion in comparison to said uncoated implantablemedical device.